JPH0830152B2 - Reactive dye, its manufacturing method and its use - Google Patents

Description

The invention relates to a novel reactive dyestuff, a process for its preparation and its use for dyeing or printing textile materials.

In the field of dyeing using reactive dyes, the level of demand for dyeing quality and the economics of dyeing methods has recently become higher. Therefore, there is a need for new reactive dyes with improved properties, especially with regard to their use.

In order to dye cotton by the room temperature pad batch method, a novel reactive dye which has sufficient direct dyeability to adapt to a low dyeing temperature and at the same time can wash off the non-fixed portion well is currently required. Further, this dye is required to have high reactivity so that the residence time is short. It must be able to give dyeings with a high fixation rate. Conventionally known dyes cannot sufficiently satisfy these requirements.

Therefore, it is an object of the present invention to provide a new and improved reactive dye suitable for the cold pad batch process, which has a high degree of the above-mentioned required properties. Such novel dyes must have the characteristics of particularly high fixation as well as high fiber-dye bond stability. In addition, the part that is not fixed to the fiber should be easy to wash off. Moreover, the dyeing fastness must be excellent overall, for example to give dyeings having good lightfastness and wetfastness.

It has now been found, according to the present invention, that the above objects are achieved by the novel reactive dyes defined in detail below.

The reactive dye of the present invention has the formula {In the formula, K is a residue of a benzene-based, naphthalene-based, phenylazonaphthalene-based or pyrazolone-based coupling component, U is -CO-, and R is a formula [Wherein Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acetoxyethyl, β-halogenethyl or vinyl, and a1k is a polymethylene group having 1 to 6 carbon atoms or its Means a branched isomer, Y is hydrogen, V is hydrogen, an alkyl group having 1 to 4 carbon atoms,
Or expression (Wherein Z, a1k and Y have the above meanings)], r is 1 or 2, X is a triazine or pyrimidine heterocyclic reactive group,
Or when K is a phenylazonaphthalene group, a halopropionyl or haloacryloyl group or a group -U-
R or —SO ₂ Z, where R, U and Z have the meanings given above, and the benzene group A is unsubstituted or additionally C _1-4 alkyl, C _1-4 alkoxy, halogen. ,
Substituted by hydroxy, carboxy and sulfo}.

The dye of formula (2a) may contain substituents customary in azo chemistry attached to its basic skeleton.

 The examples of the substituents that may be present in the dye D are shown below.

An alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl,
An alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, an acylamino group having 1 to 8 carbon atoms such as acetylamino, propionylamino, benzoylamino, amino, 1 to 4 An alkylamino group having carbon atoms such as methylamino, ethylamino, propylamino, isopropylamino or butylamino, phenylamino, N, N-di-β-hydroxyethylamino, N, N-di-β-sulfatoethyl amino,
Sulfobenzylamino, N, N-disulfobenzylamino, alkylcarbonyl having 1 to 4 carbon atoms in the alkoxy group such as methoxycarbonyl or ethoxycarbonyl, alkylsulfonyl having 1 to 4 carbon atoms such as methylsulfonyl or Ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen such as fluorine, chlorine, bromine, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl group such as N-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl N-alkylsulfamoyl having 1 to 4 carbon atoms such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-alkylsulfamoyl Butylsulfamoyl, N-
(Β-hydroxyethyl) -sulfamoyl, N, N-di- (β-hydroxyethyl) -sulfamoyl, N-phenylsulfamoyl, ureido, hydroxy, carboxy, sulfomethyl or sulfo.

Preferably the dye contains one or more sulphonic acid groups. Particularly preferred substituents in the dye are methyl, ethyl, methoxy, ethoxy, acetylamino, benzoylamino, amino, chlorine, bromine, ureido, hydroxy, carboxy, sulfomethyl or sulfo.

A β-chloroethyl group is especially considered as β-halogenethyl for Z. The polymethylene group a1k is preferably methylene, ethylene, methylmethylene, propylene or butylene. When V is an alkyl group it can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. Examples of derivatives of carboxy or sulfo groups are carbamoyl, N-methyl-, N-ethyl-, N, N-dimethyl- and N, N-diethylcarbamoyl, cyano, acetyl, propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl, Propyloxycarbonyl,
And sulfamoyl, N-methyl-, N-ethyl, N, N-dimethyl- and N, N-diethylsulfamoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl and the like.

Reactive groups X are especially low molecular weight, alkanoyl or alkylsulphonyl groups, optionally substituted by removable groups or removable groups; low molecular weight, optionally removable groups or removable groups. An alkenoyl or alkenesulfonyl group substituted by a group; a carbocyclic or heterocyclic 4-membered, 5-membered or 6-membered ring substituted by an atom or a group capable of leaving via a carbonyl or sulfonyl group Groups containing; triazine or pyrimidine groups, optionally substituted by a removable atom or a removable group, directly bonded via a carbon atom, or those containing such a group. Examples of such a reactive group include a 6-membered halogen atom-containing heterocyclic group bonded via an amino group, such as a halogen triazine group or a halogen pyrimidine group, or an aliphatic acyl group such as a halogen propionyl group. A halogen acryloyl group, or a directly bonded β-halogenethyl-sulfonyl group, β-sulfatoethylsulfonyl group or vinylsulfonyl group. Thus, the reactive group X may be attached to the basic skeleton of the dye via the amino group, or may otherwise be attached to the basic skeleton of the dye, for example by direct bonding.

The group K may again contain an azo group. That is, it may be a residue of an azo compound or a monoazo compound. K
When is a residue of a benzene- or naphthalene-based coupling component, K is preferably a benzene group, a naphthalene group, an azobenzene group, a naphthylazobenzene group,
It means an azonaphthalene group or a phenylazonaphthalene group, and may be further substituted as described later.

As K, in particular, an aminonaphtholsulfonic acid-based component as described later is considered. When K is a residue of a heterocyclic coupling component, a pyrazolone group or a pyridone group or a residue of a heterocyclic coupling component described below is considered. In this case too, the residue K may additionally contain an azo group. An example is when K is a phenylazopyrazolone group.

Further preferred among the reactive dyes of the present invention are shown below: _Where R ₂ represents hydrogen, C _1-4 -alkyl, C _1-4 -alkoxy, halogen, hydroxy, carboxy or sulfo, and K, U, R, X, r are of formula (2a) A dye having the meaning described above); Where R ₃ is hydrogen, or optionally substituted C
_1-4 -alkyl, wherein R ₂ , U, R and X have the meanings given in formula (3)); (Wherein R ₂ , U, R, and X have the meanings given in formula (3)); (Wherein R ₂ , U, R and X have the meanings given in formula (3)); (Wherein R ₄ represents 0 to 2 substituents selected from the group consisting of C _1-4 -alkyl, C _1-4 -alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X
Has the meaning described in formula (3)); (Wherein R ₅ represents 0 to 2 substituents selected from the group consisting of C _1-4 -alkyl, C _1-4 -alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X
Has the meaning described in formula (3)); (Wherein R ₅ represents 0 to 2 substituents selected from the group consisting of C _1-4 -alkyl, C _1-4 -alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X
Has the meaning described in formula (3)); in formulas (2a) to (9), a compound in which Z is a β-sulfatoethyl group, a β-chloroethyl group or a vinyl group is particularly preferable.

The feature of the method for producing the reactive dye of formula (2a) is Or a precursor thereof to react with reactive components to introduce groups R and X to form a reactive dye of formula (2a) or to convert the resulting intermediate product to the desired target dye, and In some cases, this may be followed by another conversion reaction.

If a precursor is used instead of the dye of formula (10), the target dye is completed by further reacting its intermediate product, for example by carrying out a condensation, coupling or other conversion reaction. .

The preferred azo dyes of formulas (2a) to (9) can be prepared in the following manner.

A diazo component already containing the group -U-R, i.e. Or Starting from a compound of formula (III), which is diazotized, and which also already contains a group X, for example containing a β-sulfatoethylsulfonyl group or a vinylsulfonyl group, or a halogenpyrimidinyl group or a halogentriazinylamino group. Or afterwards a reaction component such as α, β-dibromopropionyl chloride, 2,4,6-trichloro-s-triazine, 2,4-difluoro-6-amino-s-triazine or 2,4 Coupling with a coupling component containing an amino group that can be acylated with 6,6-trifluoro-5-chloropyrimidine.

In the case of the disazo dyes of formula (8) and formula (9),
The reactive group X is bonded to the diazo component as well as the coupling component. In this case too, it is possible to start from a diazo component which already contains the radical X, for example 1-amino-3-vinylsulfonylbenzene,
Alternatively, it is also possible to use a diazo component which is able to introduce the radical X after the coupling is complete. For example, 1,3-phenylenediamine-4-sulfonic acid is followed by 2,4-dichloro-6-3'-sulfophenylamino-
It may be acylated with s-triazine.

When the reactive group X contains two or more eliminable substituents such as a halogen atom, the group X
Can be condensed with a compound of formula (11) or formula (12) to replace one halogen atom with the corresponding reactive amino group. That is, for example, the group RU in the diazo component
In addition to −, the formula attached to the coupling component Reactive dyestuffs of the formula (3) containing groups of are obtained. In addition, a -N (alkyl)-group may be present as a binding member instead of the -NH- group.

Specific examples of the starting materials that can be used depending on the structure of the desired target compound are listed below.

Compound of formula (11) and its N-alkyl derivative 3-alkylbenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide, 4-chloro-3-aminobenzoic acid-N'-β- ( β'-
Chloroethylsulfonyl) -ethylamide, 4-methyl-3-aminobenzoic acid-N'-β- (β'-
Chloroethylsulfonyl) -ethylamide, 4-methoxy-3-aminobenzoic acid-N'-β- (β '
-Chloroethylsulfonyl) -ethylamide, 3-aminobenzoic acid-N'-β- [β '-(β "-chloroethylsulfonyl) -ethyloxy] -ethylamide, 3-aminobenzoic acid-N'-γ- (β '-Chloroethylsulfonyl) -propylamide, 3-aminobenzoic acid-N'-bis- [β- (β'-chloroethylsulfonyl) -ethyl] -amide, 3-aminobenzoic acid-N'-bis- [ γ- (β′-Chloroethylsulfonyl) -propyl] -amide, 3-N-ethylaminobenzoic acid-N′-β- (β′-chloroethylsulfonyl) -ethylamide, 3-N-isopropylaminobenzoic acid- N'-β-
(Β'-chloroethylsulfonyl) -ethylamide, 3-N-isopropylaminobenzoic acid-N'-γ-
(Β'-chloroethylsulfonyl) -propylamide, 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide, 4-aminobenzoic acid-N'-β- [β '-( β ″ -chloroethylsulfonyl) -ethyloxy] -ethylamide, 4-aminobenzoic acid-N′-γ- (β′-chloroethylsulfonyl) -propylamide, 4-aminobenzoic acid-N′-bis- [β- (Β′-Chloroethylsulfonyl) -ethyl] -amide, 4-aminobenzoic acid-N′-bis- [β- (β′-chloroethylsulfonyl) -propyl] -amide, 4-N-ethylaminobenzoic acid -N'-β- (β'-chloroethylsulfonyl) -ethylamide, 4-N-isopropylaminobenzoic acid-N'-γ-
(Β′-chloroethylsulfonyl) -propylamide, 4-aminobenzoic acid-N′-β- (vinylsulfonyl)
-Ethylamide, 4-aminobenzoic acid-N'-bis- [β- (vinylsulfonyl) -ethyl] -amide, 4-aminobenzoic acid-N'-δ- [β'-chloroethylsulfonyl) -butylamide, 4 -Chloro-3-aminobenzoic acid-N'-bis- [β-
(Β'-Chloroethylsulfonyl) -ethyl] -amide, 4-methyl-3-aminobenzoic acid-N'-bis- [β-
(Β′-Chloroethylsulfonyl) -ethyl] -amide, 4-methoxy-3-aminobenzoic acid-N′-bis- [γ
-(Β'-chloroethylsulfonyl) -propyl] -amide, 3-aminobenzoic acid-N'-δ- (β'-chloroethylsulfonyl) -butylamide, 3-aminobenzoic acid-N'-β- [β ′-(Β ″ -chloroethylsulfonyl) -ethyloxy] -ethylamide, 4-hydroxy-3-aminobenzoic acid-N′-β-
(Β'-Chloroethylsulfonyl) -ethylamide, 4-hydroxy-3-aminobenzoic acid-N'-bis-
[Β- (β′-chloroethylsulfonyl) -ethyl]-
Amide, 4-methoxy-3-aminobenzoic acid-N'-bis- [β
-(Β'-Chloroethylsulfonyl) -ethyl] -amide, as well as the corresponding compounds in which the β-chloroethylsulfonyl group is replaced by β-sulfatoethylsulfonyl or vinylsulfonyl; also the following are considered: 4 -Amino-3-sulfobenzoic acid-N'-β- (β'-
Chloroethylsulfonyl) -ethylamide, 4-amino-3-sulfobenzoic acid-N'-β- (β'-
Sulfatoethylsulfonyl) -ethylamide, 4-amino-3-sulfobenzoic acid-N′-β-vinylsulfonyl-ethylamide, 3-amino-2-sulfobenzoic acid-N′-β-vinylsulfonyl-ethylamide, 3- Amino-4-methoxybenzoic acid-N'-β- (β '
-Sulfatoethylsulfonyl) -ethylamide, 4-amino-3-sulfobenzoic acid-N'-bis- (β '
-Vinylsulfonyl-ethyl) -amide, 3-amino-4-methoxybenzoic acid-N'-bis- [β
-(Β'-sulfatoethylsulfonyl) -ethyl]-
Amide, 3-amino-2-sulfobenzoic acid-N'-bis- (β-
Vinylsulfonyl-ethyl) -amide, 3-amino-4-methoxybenzoic acid-N '-(γ-vinylsulfonyl-propyl) piperazide, 4-amino-3-methoxybenzoic acid-N'-bis- (β
-Vinylsulfonyl-ethyl) -amide, 3-aminobenzoic acid-N'-β- (β'-vinylsulfonyl-ethylamino) -ethylamide, 3-amino-4-methylbenzoic acid-N '-(β-vinyl Sulfonyl-ethyl) -piperazide, 4-amino-3-sulfobenzoic acid-N'-bis- [β-
(Β′-Sulfatoethylsulfonyl) -ethyl] -amide, 3-amino-4-methoxybenzoic acid-N′-bis- (β
-Vinylsulfonyl-ethyl) -amide, 3-amino-4-methoxybenzoic acid-N '-(β-vinylsulfonyl-ethyl) -amide, 4-amino-3-sulfobenzoic acid-N'-(γ-vinyl Sulfonyl-propyl) -piperazide, 4-amino-3-sulfobenzoic acid-N'-β- (β'-
Vinylsulfonyl-ethylamino) -ethylamide, 3-amino-4-methylbenzoic acid-N'-β- (β'-
Sulfatoethylsulfonyl) -ethylamide, 4-amino-3-sulfobenzoic acid-N′-bis- [β-
(Β′-Chloroethylsulfonyl) -ethyl] -amide, 4-amino-3-sulfobenzoic acid-N ′-(β-vinylsulfonyl-ethyl) -piperazide, 4-amino-3-sulfobenzoic acid-N ′ -Β- (β'-
Vinylsulfonyl-ethylamino) -ethylamide, 5-amino-1,3-benzenedicarboxylic acid-N ', N "-
(Β-Vinylsulfonyl-ethyl) -diamide, 4-amino-3-sulfobenzoic acid-N′-β- (β′-
Vinylsulfonyl-ethyloxy) -ethylamide, and further aminobenzoic acid amides or aminobenzenesulfonic acid amides similar to the following amino compounds: β- [β ′-(β ″ -chloroethylsulfonyl) -ethylamino] -ethylamine, β- ( β'-vinylsulfonyl-ethylamino) -ethylamine, β- [β '-(β "-sulfatoethylsulfonyl)-
α'-methyl-ethylamino] -ethylamine, β- [β '-(β "-sulfatoethylsulfonyl)-
α'-methyl-ethylamino] -β-methylethylamine, γ- [β '-(β "-sulfatoethylsulfonyl)-
α'-methyl-ethylamino] -propylamine, δ- [β '-(β "-sulfatoethylsulfonyl)-
α'-Methyl-ethylamino] -n-butylamine.

Suitable diazo components are also suitable compounds of the aminobenzene or aminonaphthalene type. For example, compounds such as those contained in the azo dyes of the above formula. Examples are: 1,3-diamino-benzene, 1,4-diamino-benzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3 -Diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene 1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1, 4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 2,6-diaminonaphthalene, 1,3 -Diamino-2,4,6-trimethylbenzene, 1,4- Amino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4'-diaminostilbene, 4,4'-diamidiphenylmethane, 4,4'-diabibiphenyl ( Benzidine) 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3,3′-dichlorobenzidine, 3,3′-dicarboxybenzidine, 3,3′-dicarboxymethoxybenzidine, 2,2 ′ -Dimethylbenzidine, 4,2'-diaminodiphenyl (diphenylene), 2,6-diaminonaphthalene-4,8-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2, 5-disulfonic acid, 1,4-diaminobenzene-2,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diamino -2-Chlorobenzene-5 Rufonic acid, 1,4-diamino-2-methylbenzene-5-sulfonic acid, 1,5-diamino-6-methylbenzene-3-sulfonic acid, 1,3-diamino-6-methylbenzene-4-sulfonic acid , 3, (3'- or 4'-aminobenzoylamino) -1
-Amino-benzene-6-sulfonic acid, 1- (4'-aminobenzoylamino) -4-aminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2-carboxylic acid, 1,3-diamino Benzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene, 4,4'-diaminodiphenyl oxide 4,4'-diaminodiphenyl-urea-2,2'-disulfonic acid, 4,4'-diaminodiphenyloxyethane-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'- Disulfonic acid, 4,4'-diaminodiphenylethane-2,2'-disulfonic acid, 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulfone Acid, 1 Amino-4-methoxy-5-aminomethyl-benzene-6-sulfonic acid, 1,3,5-triaminobenzene.

One or two linked formulas Z which can be used as diazo component for the preparation of mono- or disazo dyes
Examples of aromatic amines containing the group —SO ₂ are: 1-amino-4-β-sulfatoethylsulfonylbenzene, 1-amino-4-β-thiosulfatoethylsulfonylbenzene. 1-amino-4-vinylsulfonylbenzene, 1-amino-4-β-chloroethylsulfonylbenzene, 1-amino-3-β-sulfatoethylsulfonylbenzene, 1-amino-3-vinylsulfonylbenzene, 1- Amino-2-methoxy-5-β-sulfatoethylsulfonylbenzene, 1-amino-2-methoxy-5-β-thiosulfatoethylsulfonylbenzene, 1-amino-2-methoxy-5-vinylsulfonylbenzene, 1 -Amino-4-methoxy-3-β-sulfatoethylsulfonylbenzene, 1-amino-4-methoxy- -Β-vinylsulfonylbenzene, 1-amino-2,5-dimethoxy-4-β-sulfatoethylsulfonylbenzene, 1-amino-2,5-dimethoxy-4-vinylsulfonylbenzene, 1-amino-2-methoxy -4-β-Sulfatoethylsulfonyl-5-methylbenzene, 1-amino-2-methoxy-4-vinylsulfonyl-5
-Methylbenzene, 1-amino-3-β-sulfatoethylsulfonyl-6
-Carboxybenzene, 1-amino-3-vinylsulfonyl-6-carboxybenzene, 1-amino-4-β-sulfatoethylsulfonylbenzene-2-sulfonic acid 1-amino-4-vinylsulfonylbenzene-2-sulfonic acid 1-amino-5-vinylsulfonylbenzene-2,4-disulfonic acid, 1-amino-2-hydroxy-5-β-sulfatoethylsulfonylbenzene, 1-amino-2-hydroxy-4-β-sulfato Ethylsulfonylbenzene, 1-amino-2-hydroxy-5-β-sulfatoethylsulfonylbenzene-3-sulfonic acid, 1-amino-2-bromo-4-β-sulfatoethylsulfonylbenzene, 1-amino-2 , 6-Dichloro-4-β-sulfatoethylsulfonylbenzene, 1-amino-2,4-di- (β- Rufatoethylsulfonyl) -benzene, 1-amino-2,4-di- (β-sulfatoethylsulfonyl) -5-chlorobenzene, 1-amino-2,4-di- (β-thiosulfatoethylsulfonyl) ) -5-Chlorobenzene, 1-amino-2,4-di- (vinylsulfonyl) -chlorobenzene, 1-amino-2,4-di- (vinylsulfonyl) -5-chlorobenzene, 1-amino-2 , 4-di- (β-acetoxyethylsulfonyl) -benzene, 1-amino-2,4-di- (β-acetoxyethylsulfonyl) -chlorobenzene, 2-amino-8-β-sulfatoethylsulfonylnaphthalene, 2-Amino-6-β-sulfatoethylsulfonylnaphthalene, 2-amino-6-β-sulfatoethylsulfonylnaphthalene-1-sulfonic acid, 2-amino-8-β-su Rufatoethylsulfonylnaphthalene-6-sulfonic acid, 2-amino-6,8-di- (β-sulfatoethylsulfonyl) -naphthalene.

Further examples are the corresponding β-hydroxy compounds which can be used as precursors. For example: 1-amino-4-β-hydroxyethylsulfonylbenzene, 1-amino-3-β-hydroxyethylsulfonylbenzene, 1-amino-2,4-di- (β-hydroxyethylsulfonyl) -Benzene, 1-amino-2,4-di- (β-hydroxyethylsulfonyl) -5-chlorobenzene.

When an amino-acetylamino compound whose acetyl group can be eliminated later by saponification instead of diamine as described above is used as the diazo component,
Monoacetyl compounds of the diazo component exemplified above are also considered. For example, 1-acetylamino-3-aminobenzene-4-sulfonic acid or 1-acetylamino-4
-Aminobenzene-3-sulfonic acid.

Suitable as coupling components are especially aminobenzene- and naphthalene-based compounds. For example,
Aniline, N-monosubstituted aniline, m-phenylenediamine derivative, aminonaphthalene, naphthol, aminonaphthalenesulfonic acid, naphtholsulfonic acid or aminonaphtholsulfonic acid, and further pyrazolone, aminopyrazole, aminopyridine, hydroxypyridine / pyridone, aminopyrimidine. , Hydroxypyrimidine, indole, barbituric acid derivative or acetoacetoarylide. Specific examples are given below: 1-amino-3-methyl-benzene, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino -3-Acetyl-aminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-sulfonic acid, 1-amino-2 -Methoxy-naphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfone Acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl or 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl or 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1 -Amino-5-hydroxy-naphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or
4,6-Disulfonic acid, 1- (4'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2- (4'-amino-3'-sulfophenylamino ) −
5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 2,4,6-triamine-3-cyanopyridine, 1-β-aminoethyl-3-cyano-4- Methyl-6-
Hydroxypyridone (2), 1-γ-aminopropyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2), 1,3-diaminobenzene, 1-amino-3- (N, N-di- β-hydroxyethylamino) -benzene, 1-amino-3- (N, N-di-β-sulfatoethylamino) -benzene, 1-amino-3- (N, N-di-β-hydroxyethylamino ) -4-Methoxybenzene, 1-amino-3- (N, N-di-β-sulfato-ethylamino) -4-methoxybenzene, 1-amino-3-sulfo-benzylamino-benzene, 1-amino- 3-sulfo-benzylamino-4-chloro-benzene, 1-amino-3- (N, N-disulfo-benzylamino)
-Benzene, 1- (3'-aminophenyl) -3-methyl-5-pyrazolone as well as 1- (aminophenyl) -3-carboxy-5-pyrazolone, which in the phenyl nucleus are chlorine, methyl, methoxy, nitro or Optionally substituted by sulfo, as well as 1- (2'-sulfo-4'-aminophenyl) -3-carboxy-pyrazolone- (5).

When one of the two components contains two reactive groups at the same time or when the two reactive groups can be introduced into the corresponding component, for example, as a coupling component, the compound of formula (11)
When the compound of 1 is used, the other component (in this case the diazo component) may be non-reactive, for example the following compounds: aminobenzene, 1-amino-2-,- 3- or -4-methylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5 -Dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 2-aminodiphenyl ether , 1-aminobenzene-2-, -3- or -4-sulfonic acid amide, 1-aminobenzene-2-, -3- or -4-carboxylic acid, dehydrothio-p-toluidine- Sulfonic acid, 1-amino-3-trifluoromethylbenzene-6-sulfonic acid, 1-aminobenzene-2-, -3- or -4-sulfonic acid, 1-aminobenzene-2,4- and -2, 5-disulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid 1-amino-2-carboxybenzene-4-sulfonic acid, 1-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or -5-chlorobenzene-2-sulfonic acid, 1-amino -6-chlorobenzene-3- or -4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-5-methyl-4-chlorobenzene-2- Sulfonic acid, 1-amino-4- or -5-methoxybenzene-2-
Sulfonic acid, 1-amino-6-methoxybenzene-3- or -4-
Sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-
Sulfonic acid, 1-amino-2,4-dimethoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfonic acid 1-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-acetylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid, 2-Amino-1-methylbenzene-3,5-disulfonic acid, 1-amino-4-methoxybenzene-2,5-disulfonic acid, 1-amino-3- or -4-nitrobenzene-6-sulfonic acid, 1 -Aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene-2-,-4-,-5, -6
-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -3-, -4-, -5
-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-3,6- or -5,7-disulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfone Acid, 2-aminonaphthalene-1,5-,-1,7-,-3,6-,-
5,7-, -4,8-, or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, -3, 6,8- or -4,
6,8-Trisulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-4,6-disulfonic acid, 1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, 1-hydroxy-2-amino-6-acetylaminobenzene-4 -Sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5
-Sulfonic acid, 1-hydroxy-2-amino-4-methylsulfonylbenzene, 1-amino-2-hydroxy-6-nitronaphthalene-
6-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, 3-methoxy-4-amino-6-methoxyazobenzene-2 ', 4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-
2 ', 5'-disulfonic acid. The diazotization of the diazo component or the diazotization of an intermediate product containing a diazotizable amino group is generally carried out in an aqueous mineral acid solution at low temperature with nitrous acid. Coupling to the coupling component is carried out at strongly acidic, neutral to weakly alkaline pH values.

When X is a reactive group bonded via an amino group, a monoazo- or disazo intermediate product capable of being condensed or acylated with the corresponding reactive group and a diazo component or a coupling component or an amino group-containing dye or Condensation with the precursor is preferably carried out in an aqueous solution or suspension at low temperature and at weakly acidic, neutral to weakly alkaline pH values. It is advantageous to neutralize the hydrogen halide liberated during the condensation by continuously adding an alkali metal salt hydroxide, carbonate or hydrogen carbonate.

One embodiment of the process is a process in which a dye containing a precursor of a reactive group is first prepared and subsequently converted into a target substance, for example by esterification or addition reaction. Example, Z is _{HO-CH 2 CH 2 -SO 2} -
The basic dyestuff is prepared and this intermediate product is reacted with sulfuric acid either before or after acylation to convert the hydroxy groups to sulfato groups. Alternatively, the Z is
_{H 2 C = CH-SO 2} - Using an analogous dye is, the intermediate product by adding a thiosulfate based on _{HO 3 SS-CH 2 CH 2} -SO 2 - is to produce an.

Sulfation of the hydroxy groups in the dye of formula (2a) or a suitable precursor is preferably carried out by reacting with concentrated sulfuric acid at 0 ° C. to a moderately elevated temperature.

This sulfation can also be carried out by reacting the hydroxy compound with 2 moles of chlorosulfonic acid per mole of hydroxy group in a polar organic solvent such as N-methylpyrrolidone at 10-80 ° C. Sulfation is preferably carried out by introducing the compound of interest into sulfuric acid monohydrate at a temperature of 5 to 15 ° C.

The introduction of another group such as a thiosulfone group or a phosphato group instead of a halogen atom or a sulfato group as Z in the compound of formula (2a) or the intermediate product can be carried out by a method known per se.

Furthermore, the elimination reaction can be performed after the synthesis. For example, a reactive dye of formula (2a) containing a sulfatoethylsulfonyl group may be treated with a hydrohalide-eliminating agent such as sodium hydroxide to convert the sulfatoethylsulfonyl group to a vinylsulfonyl group. it can.

In some cases, variations starting from dye precursors can be used. This variant is of the formula (2a) in which D is the residue of a dye synthesized from two or more components, for example the residue of an anthraquinone dye of the bromamic acid type, a copper or nickel phthalocyanine or a copper formazan type dye. It is particularly suitable for the production of reactive dyes. In principle, the reactive dyes of the formula (2a) of all dye classes are prepared by known methods or by analogy with known methods starting from precursors or intermediates containing fiber-reactive groups according to the formula (2a). Alternatively, it can be prepared by introducing such a fiber-reactive group into an intermediate product having appropriate dye characteristics.

When a group having a metal complex-forming ability is present in the produced reactive dye, the reactive dye can be subsequently metallized.

Important embodiments of the method according to the invention are shown in the examples below.

Further, in the present invention, compounds of the following formula are particularly important.

In the formula, R and U have the meanings described in formula (2a).

The compound of formula (11) can be produced by the following method.

That is, the corresponding aminobenzoic acid chloride or aminonaphthoic acid chloride or the corresponding sulfonic acid chloride is condensed with the amine corresponding to the residue of formula (1a); or alternatively nitrobenzoyl chloride or nitronaphthoyl chloride. Starting from the compound or -sulfochloride, condensing with the amine and reducing the nitro group to the amino group. The acid chloride is also reacted with an unsaturated aliphatic amine and the double bond of the acid amide is reacted with 50 to 180 by the method described in another German published patent application 2040620.
The 2-marker ethanol can be added with a radical former or a catalytic amount of sulfur at a temperature of ° C. The hydroxyethyl thioether compound thus obtained can also be prepared by condensing the acid chloride with a halogenalkylamine and heating the condensation product with 2-markaptoethanol and sodium alcoholate in an alcohol. This thioether compound is further oxidized to the corresponding sulfone.

The oxidation of the thioether compound to the sulfone can be carried out by various methods. For example, with hydrogen peroxide with or without the addition of tungsten or vanadium compounds as catalyst, or with peracetic acid, potassium permanganate or chromic acid, or with chlorine and / or hydrochloric acid, It can be carried out in aqueous, aqueous-organic or organic medium, respectively.

Carboxylic acid amides or sulfonic acid amides in which the group —SO ₂ —Z means a β-hydroxyethylsulfonyl group, obtained by such a method, are sulfating agents, phosphorylating agents, halogenating agents, alkyl or aryl sulfones. By treatment with an acid halide, an alkyl or aryl carboxylic acid halide or an alkyl or aryl carboxylic acid anhydride, the group --SO ₂ --Z is converted to --S
_{O 2 -CH 2 -CH 2 -O-} SO 3 H, SO 2 -CH 2 -CH 2 -O-PO 3 H 2,
-SO ₂ -CH ₂ -CH ₂ - halogen or -SO ₂ -CH ₂ -CH _2, -
It is converted to the corresponding dye precursor meaning O-acyl. The product thus obtained is further treated with an alkali agent such as an alkali metal hydroxide or carbonate such as sodium hydroxide or sodium carbonate to give the group --SO ₂ --Z the group SO ₂ --CHCH. It can be converted to the corresponding compound meaning ₂ . Further, the product thus obtained is reacted with (addition to) a salt of thiosulfate such as sodium thiosulfate, or a dialkylamine such as dimethylamine or diethylamine, or phenol to give a group --SO ₂ Z, respectively.
_{SO 2 -CH 2 -CH 2 -S-} SO 3 H, -SO 2 -CH 2 -CH 2 -N ( alkyl) _2, or, Can be converted into a compound meaning.

Suitable sulfating agents in this case are, for example, concentrated sulfuric acid, chlorosulfonic acid, amidosulfonic acid or other compounds which release sulfur trioxide. Suitable phosphorylating agents are
For example, concentrated phosphoric acid, pillows, meta- or polyphosphoric acid, polyphosphoric acid alkyl esters, phosphorus oxychloride or a mixture of phosphoric acid and phosphorus (V) oxide. As the halogenating agent, for example, thionyl chloride or thionyl bromide can be used.

 Preferred compounds are of the formula:

R in the formula means a residue of the formula: Wherein U, Z, alk, Y and V have the meanings given above in formula (2a): R ₂ is hydrogen, C _1-4 -alkyl, C _1-4 -alkoxy, halogen, hydroxy, carboxy or Means sulfo.

The features of the preferred method for producing the compound of formula (14) are: The nitrobenzoyl chloride of the formula Of the nitro group to the amino group.

The reaction is preferably carried out in a high boiling organic solvent such as nitrobenzene. The reduction of the nitro group to the amino group is carried out in a manner known per se by catalytic hydrogenation using Pd / carbon in ethanol, acetoacetate or tetrahydrofuran at temperatures from room temperature to about 40 ° C. This reduction can also be carried out using Fe / hydrochloric acid in aqueous solution.

The compound of formula (14) can also be produced by a modification of the above-mentioned production method as follows. That is, the formula (1
5) nitrobenzoyl chloride, the formula Of the above-mentioned amine, the condensation product is oxidized with the elemental chlorine to the corresponding β-chloroethylsulfonyl compound and the nitro group is reduced to the amino group.

The condensation of the amine of formula (20) with nitrobenzoyl chloride is carried out, for example, in chloroform at room temperature in the presence of an alkaline acid binder such as a hydroxide, carbonate or bicarbonate of an alkali metal salt. The condensation product is then oxidized in a manner known per se using a chlorine / hydrochloric acid mixture. Reduction of the nitro group to the amino group is carried out by the method described above.

The amines of formulas (16) and (20) used as starting compounds can be prepared according to the procedure of Example 1 of West German Patent Publication No. 2614550.

The bracketed portion of the above formula (2a) is a reactive group, and there may be one or two in the molecule.

When n = 2 or r = 2, the corresponding reactive groups may be the same or different from each other. It is preferred that both groups are the same. The reactive group contains a substituent that is a fiber-reactive leaving group (eg, when Z is β-chloroethyl) or a substituent that can behave similarly to a fiber-reactive leaving group (eg, Z is For vinyl). The fiber-reactive compound reacts by forming a covalent chemical bond with a hydroxyl group of cellulose, an amino group, a carboxy group, a hydroxyl group or a thiol group in the case of wool or silk or an amino group of a synthetic polyamide and, in some cases, a carboxy group. It should be understood as a possible compound.

The reactive dye of the formula (2a) is suitable for dyeing and printing various fiber materials such as silk, leather, wool, polyamide fiber, polyurethane and cellulose-containing fiber materials. In particular, it is suitable for dyeing and printing all types of cellulose-containing fiber materials, for example, natural cellulosic fibers such as cotton, hemp and flax, as well as pulp and regenerated cellulose. The reactive dyestuffs of the formula (2a) are also suitable for dyeing and printing hydroxyl group-containing fiber materials contained in mixed fabrics, for example cotton and polyester or cotton and polyamide.

The dyes of the invention can be applied to the fiber material and fixed to the fiber in various ways. In particular, it can be applied in the form of an aqueous dyeing solution or an aqueous printing paste. The dye is suitable for both the exhaustion method and the pad dyeing method. In the latter case,
The article to be dyed is optionally impregnated with an aqueous dye solution containing a salt and fixed after alkali treatment or in the presence of alkali, optionally under the action of heat. However,
The dye is particularly suitable for use in the so-called room temperature pad batch method. In this dyeing method, the dye is applied on a spread with an alkali and left at room temperature for several hours to be fixed. After fixing, the dye or print is rinsed thoroughly with cold and warm water, optionally with the addition of agents which have a dispersing effect and which promote the diffusion of the non-fixed parts.

The reactive dye of the formula (2a) has high reactivity and good fixing properties. Therefore, a low dyeing temperature can be used in the exhaust method, and a steaming time can be shortened in the pad-steam method. The sticking rate is high and the non-sticking portion can be easily washed off. in this case,
The difference between the exhaustion rate and the sticking rate is extremely small. That is, the soaping loss is very small. The reactive dyes of the formula (2a) are also suitable for printing, especially for printing cotton. However, it is also applicable to the printing of nitrogen-containing fiber materials such as wool, silk or wool blend fabrics.

Dyes and prints produced by dyeing or printing a cellulose-containing fiber material with the dye of the present invention have high color density and high fiber-dye bond stability in both acidic and alkaline regions. Furthermore, it has good light fastness and also wash light fastness, water fastness, seawater fastness,
Very good wet fastness such as overlay resistance and sweat fastness. It also has excellent fold, iron and rubbing fastness.

 An example for explaining the present invention will be described below.

Parts are parts by weight and percentages are percentages by weight, unless stated otherwise. The relationship between parts by weight and parts by volume is the same as the relationship between kilograms and liters.

The preparation of monoazo- and disazo intermediate compounds is not necessarily described in full in the examples below, but their preparation will be apparent from the general description given above.

Example 1 4-Aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a solution of hydrochloric acid-acidic diazotization in 1- (2) at a temperature of 0 to 5 ° C and a pH of 5 to 6 ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. The yellow monoazo dye formed is then added with a suspension of 18.8 parts of cyanuric chloride and acylated at pH 6.

Therefore, a chlorotriazine dye corresponding to the following formula is produced and is isolated.

Example 2 4-Methoxy-3-aminobenzoic acid-N'-β-
A solution of 35.7 parts of (β'-chloroethylsulfonyl) -ethylamide hydrochloride in acid diazotized hydrochloric acid was added to 1- (2'-sulfo-5'-aminophenyl) -3-carboxy at a temperature of 0 to 5 ° C and a pH of 5 to 6. Coupling is performed by adding 29.9 parts of 5-pyrazolone. The yellow monoazo dye formed is then added with a suspension of 18.8 parts of cyanuric chloride and acylated at pH 6. Then 10.7 parts of N-methylaniline are added and a second condensation is carried out at a temperature of 20 to 30 ° C. and pH = 6.5.

Thus, a monochlorotriazine dye corresponding to the following formula is produced and is isolated.

Example 3 4-Methoxy-3-aminobenzoic acid-N'-β-
A solution of 35.7 parts of (β'-chloroethylsulfonyl) -ethylamide hydrochloride in acid diazotized hydrochloric acid was added to 1- (2'-sulfo-5'-aminophenyl) -3-carboxy at a temperature of 0 to 5 ° C and a pH of 5 to 6. Coupling is performed by adding 29.9 parts of 5-pyrazolone. A suspension of 21 parts of 2,4-dichloro-6-isopropoxy-triazine was added to the yellow monoazo dye formed, and 20 to 35
Acylation at ℃, pH = 6.

Thus, a monochlorotriazine dye corresponding to the following formula is produced and is isolated.

Example 4 4-Aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a solution of hydrochloric acid-acidic diazotization in 1- (2 at a temperature of 0 to 5 ° C and a pH of 5 to 6) ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. Next to the produced yellow monoazo dye
A suspension of 21 parts of 2,4-dichloro-6-isopropoxy-triazine is added and acylated at 20-35 ° C, pH = 6.

Thus, a monochlorotriazine dye corresponding to the following formula is produced and is isolated.

Example 5 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a solution of hydrochloric acid-acidic diazotization in 1- (2 ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. Next to the produced yellow monoazo dye
A suspension of 17 parts of 2,4,6-trifluoro-5-chloro-pyrimidine is added and acylated at room temperature and pH.

A difluorochloropyrimidine dye corresponding to the following formula is thus formed, which is isolated.

Example 6 4-Aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a hydrochloric acid diazotized solution of 1- (2 at a temperature of 0 to 5 ° C and a pH of 5 to 6 are used. ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. Next to the produced yellow monoazo dye
A suspension of 22 parts of 2,4,5,6-tetrachloropyrimidine is added and acylated at 20-35 ° C., pH = 6.

Thus, a trichloropyrimidine dye corresponding to the formula below is produced. This is isolated by a conventional method.

Example 7 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a hydrochloric acid diazotized solution of 1- (2 at a temperature of 0-5 [deg.] C. and a pH of 5-6. ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. The yellow monoazo dye formed is then added with a suspension of 18.8 parts of cyanuric chloride and acylated at pH 6. Next, add 10.7 parts of N-methylaniline
A second condensation is carried out at 20-30 ° C., pH = 6.5.

Thus, a monochlorotriazine dye corresponding to the following formula is produced and is isolated.

Example 8 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) -ethylamide hydrochloride 32.7 parts of a hydrochloric acid diazotized solution of 1- (2 at a temperature of 0 to 5 [deg.] C. and a pH of 5 to 6 are used. ′ -Sulfo-5′-aminophenyl) -3-
Coupling is performed by adding to a solution of 29.9 parts of carboxy-5-pyrazolone. The yellow monoazo dye formed is then added with 14 parts of cyanuric fluoride and acylated at pH 6. Then, 10.7 parts of N-methylaniline was added to add 0 to
A second condensation is carried out at a temperature of 20 ° C. and a pH of 6.5. The resulting monofluorotriazine dye is isolated. This dye corresponds to the following formula:

Further, in the same manner as in Example 1, useful reactive dyes of the general formula D ₁ -N = N-K-Z ₁ (1A) shown in the following table can be prepared. Code in table
D ₁ , K and Z ₁ have the meanings given in formula (1A). W _{1 to} W ₇ have the following meanings. In the last column of the table, the dyeing color when cotton is dyed with the corresponding dye is described.

Example 36 48 parts of 2-amino-5-naphthol-7-sulfonic acid
Add 30% aqueous sodium hydroxide to adjust the pH to 4.0-4.5
Dissolves in 800 parts of water. Heated to 60 ° C and 2,4,5,6-
45 parts of tetrachloropyrimidine are added dropwise. At this time, 5N sodium hydroxide solution is added dropwise to maintain the pH at 3.0 to 4.0. The condensation is carried out at this pH of 3.0 to 3.5 and a temperature of 60 ° C. for 20 hours.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 66 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
Due to the reactive dyestuffs, it is possible to dye cellulose fiber materials in an orange color with very good wet fastness by the customary dyeing and printing processes.

Example 37 48 parts of 2-amino-5-naphthol-7-sulfonic acid
Add 30% aqueous sodium hydroxide to adjust the pH to 6.0-6.5
Dissolves in 800 parts of water.

Cool to 10 ° C. and add 34 parts of 2,4,6-trifluoro-5-chloropyrimidine dropwise. At this time, 5N sodium hydroxide solution is added dropwise to maintain the pH at 6.0 to 6.5. This pH 6.
Stir for 20 minutes at 0 to 6.5 and a temperature of 15 ° C.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 66 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in orange shades with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 38 195 parts of cyanuric chloride are dissolved in 800 parts by volume of acetone. While stirring this solution well, 1300 parts of water, crushed ice 13
Place in a mixture consisting of 00 parts and 20 parts by volume of 2N hydrochloric acid. To the obtained suspension, 239 parts of 2-amino-5-naphthol-7-sulfonic acid, 65 parts of sodium carbonate and 200 parts of water were added.
50 to 6 with stirring in 0 parts pH 6.9 to 7.2 solution
Add in 0 minutes. The reaction of cyanogen chloride with aminonaphthol is carried out at 0-5 ° C and pH 3-5. Continue stirring until free amine is no longer detected as checked by the diazotized sample.

To the coupling component solution prepared above, 330 parts of diazotized 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride is added. Stir for 2 hours, during which time add sodium carbonate little by little to raise the pH to 6.5-7.0. Stir for an additional hour at this pH and room temperature. Next, aniline-m-sulfonic acid
173 parts are added and about 110 parts sodium carbonate are added in small portions to maintain the pH at 5.5-6.0. This reaction solution
Heat to 50 ° C. and hold at this temperature for 1 hour with stirring. After cooling the reaction solution, the azo compound formed is precipitated by adding sodium chloride, isolated by suction filtration and dried at 60 ° C. in vacuo.

Thus, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This azo compound is a very excellent dye. Due to its fiber reactivity it is possible to dye cotton in vivid orange shades, for example from aqueous-alkaline baths, by customary exhaust and pad processes. The color has very good washfastness and lightfastness.

Example 39 195 parts of cyanuric chloride are dissolved in 800 parts by volume of acetone. While stirring this solution well, 1300 parts of water, crushed ice 13
Place in a mixture consisting of 00 parts and 20 parts by volume of 2N hydrochloric acid. The obtained suspension was mixed with 239 parts of 2-amino-8-naphthol-6-sulfonic acid, 65 parts of sodium carbonate and 200 parts of water.
50 to 6 with stirring in 0 parts pH 6.9 to 7.2 solution
Add in 0 minutes. The reaction of cyanogen chloride with aminonaphthol is carried out at 0-5 ° C and pH 3-5. Continue stirring until free amine is no longer detected as checked by the diazotized sample.

To the coupling component solution prepared above is added 330 parts of diazotised 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride. Stir for 2 hours while gradually adding sodium carbonate to raise the pH to 6.5-7.0. Stir for an additional hour at this pH and room temperature. Next, 173 parts of aniline-m-sulfonic acid is added, and further about 110 parts of sodium carbonate is added little by little to maintain the pH at 5.5 to 6.0. The reaction solution is heated to 50 ° C. and kept at this temperature for 1 hour with stirring. After cooling the reaction solution, the azo compound formed is precipitated by adding sodium chloride, isolated by suction filtration and dried at 60 ° C. in vacuo.

Thus, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This azo compound is a very excellent dye. Due to its fiber reactivity it is possible to dye cotton in vivid orange shades, for example from aqueous-alkaline baths, by customary exhaust and pad processes. The color has very good washfastness and lightfastness.

Other valuable reactive dyes of the general formula (1A) shown in the table below were prepared according to the methods described in Examples 38 and 39. The symbols D ₁ , K, Z ₁ in the table have the meanings given in formula (1A), and W _{1 to} W ₇ have the same meanings as given for the previous table. In the last column of the table, the dyeing color when cotton is dyed with the corresponding dye is described.

Example 81 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid 31.9 parts are neutrally dissolved in 800 ml of water and the solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. To 100 ml of water was added 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride, pH
After adding the mixture adjusted to 5, the pH of the reaction mixture
For the first time, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH 5
Hold 6 through 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours.

After the reaction was completed, the intermediate product was mixed at 0 to 10 ° C and pH 6.5 for 3 times.
Coupling with 3 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) ethylamide hydrochloride. After completion of the coupling at pH 8, the reaction mixture is filtered by filtration and the reactive dye of the formula
Or concentrated by lyophilization or isolated by lyophilization.

This dye dyes cotton red.

Example 82 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water and the solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. To 100 ml of water was added 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride, pH
After adding the mixture adjusted to 5, the pH of the reaction mixture
For the first time, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH 5
Hold 6 through 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours.

After the reaction was completed, the intermediate product was mixed at 0 to 10 ° C and pH 6.5 for 3 times.
Coupling with 3 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride. After completion of the coupling at pH 8, the reaction mixture was clarified and the reaction dye of the formula
Concentrate at 7 or isolate by lyophilization.

This dye dyes cotton red.

Example 83 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 30 ° C. and add 42 parts of 2,4-dichloro-6-isopropoxy-triazine dropwise.
At this time, 5N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. 15 at this pH 4.0 to 4.5 and temperature of 65 ℃
Allow time to condense.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 56 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 84 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 30 ° C. and add 42 parts of 2,4-dichloro-6-isopropoxy-triazine dropwise.
At this time, 2N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. 15 at this pH 4.0 to 4.5 and temperature of 65 ℃
Allow time to condense.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 56 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid was added.
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain pH 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 85 1-Amino-8-naphthol-3,6-disulfonic acid 64
PH 9.0 to 30 parts by adding 30% sodium hydroxide aqueous solution.
Dissolve in 800 parts of water at 9.5. Cooled to 10 ° C and 2,4,
34 parts of 6-trifluoro-5-chloro-pyrimidine are added dropwise. At this time, 5N sodium hydroxide solution was added dropwise to adjust the pH.
Keep at 9.25 to 9.5. 15 at pH 8.5 to 9 and temperature 15 ℃
Stir for 1 minute and add 4N hydrochloric acid solution until pH 6.5.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 66 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 86 1-Amino-8-naphthol-3,6-disulfonic acid 64
PH 9.0 to 30 parts by adding 30% sodium hydroxide aqueous solution.
Dissolve in 800 parts of water at 9.5. Cooled to 10 ° C and 2,4,
34 parts of 6-trifluoro-5-chloro-pyrimidine are added dropwise. At this time, 5N sodium hydroxide solution was added dropwise to adjust the pH.
Keep at 9.25 to 9.5. 15 at pH 8.5 to 9 and temperature 15 ℃
Stir for 1 minute and add 4N hydrochloric acid solution until pH 6.5.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 66 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 87 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 30 ° C. and add 45 parts of 2,4,5,6-tetrachloro-pyrimidine dropwise. At this time, 5N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. Condensate for 15 hours at pH 4.0 to 4.5 and temperature 65 ° C.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 66 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid 4
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 88 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 60 ° C. and add 45 parts of 2,4,5,6-tetrachloro-pyrimidine dropwise. At this time, 5N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. Condensate for 15 hours at pH 4.0 to 4.5 and temperature 65 ° C.

This solution is used as the coupling component for dye preparation.

4-aminobenzoic acid for the production of diazonium compounds
66 parts of N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water and concentrated hydrochloric acid 45
Parts to acidify and add 5N sodium nitrite solution 40
Diazotization in the capacity part. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 89 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 60 ° C. and add 45 parts of 2,4,5,6-tetrachloro-pyrimidine dropwise. At this time, 2N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. Condensate for 15 hours at pH 4.0 to 4.5 and temperature 65 ° C.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 67 parts of 4-aminobenzoic acid-N'-γ- (β'-chloroethylsulfonyl) -propylamide hydrochloride was suspended in 500 parts of ice-cold water, and 45 parts of concentrated hydrochloric acid was added. Acidify and diazotize with 40 parts by volume of 5N sodium nitrite solution. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red, electrolyte-containing dye powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 90 11.9 Amino-8-hydroxynaphthalene-3,6-disulfonic acid (31.9 parts) is neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was added to 100 ml of water and adjusted to pH 5
The pH of the reaction mixture is kept constant at a weak Congo acidity by adding 2N sodium hydroxide solution to the reaction mixture for a while, and then the pH is kept at 5 to 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours.

After completion of the reaction, this intermediate product is coupled with 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride at a temperature of 0 to 10 ° C and a pH of 6.5. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 91 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was added to 100 ml of water and adjusted to pH 5
The pH of the reaction mixture is kept constant at a weak Congo acidity by adding 2N sodium hydroxide solution to the reaction mixture for a while, and then the pH is kept at 5 to 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours.

After completion of the reaction, this intermediate product is coupled with 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride at a temperature of 0 to 10 ° C and a pH of 6.5. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 92 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. After adding 11 parts of N-methylaniline to 100 ml of water and adding a mixture adjusted to pH 5, the pH of the reaction mixture is kept at a low level by adding 2N sodium hydroxide solution for the first time. After that, the pH is maintained at 5 to 6. At this time, 2-3
Raise the temperature to 20-25 ° C over time.

After completion of the reaction, this intermediate product was treated with diazotized 4-aminobenzoic acid-N'-β- at a temperature of 0 to 10 ° C and a pH of 6.5.
Coupling with 33 parts of (β'-chloroethylsulfonyl) -ethylamide hydrochloride. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 93 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. After adding 11 parts of o-toluidine to 100 ml of water and adding the mixture adjusted to pH 5, the pH of the reaction mixture was kept constant at a low Congo acidity by adding 2N sodium hydroxide solution for a while for the first time. And then hold at pH 5-6. At this time, 2
Raise the temperature to 20-25 ° C in ~ 3 hours. After the reaction is complete,
This intermediate product is coupled at a temperature of 0 to 10 ° C. and a pH of 6.5 with 33 parts of diazotised 3-aminobenzoic acid-N′-β- (β′-chloroethylsulfonyl) -ethylamide hydrochloride. After completion of the coupling reaction at pH 8, the reaction mixture was clarified by filtration and the reaction dye of the formula
The reaction solution is concentrated or isolated by lyophilization.

This dye dyes cotton red.

Example 94 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N sodium hydroxide solution is added dropwise at the same time to maintain the pH of the reaction solution at weak Congo acidity. After adding 11 parts of N-methylaniline to 100 ml of water and adding a mixture adjusted to pH 5, the pH of the reaction mixture is kept at a low level by adding 2N sodium hydroxide solution for the first time. After that, the pH is maintained at 5 to 6. At this time, 2-3
Raise the temperature to 20-25 ° C over time.

After completion of the reaction, this intermediate product was treated with diazotised 4-aminobenzoic acid-N'-bis- at a temperature of 0 to 10 ° C and a pH of 6.5.
Coupling with 49 parts of β- (bis-β′-chloroethylsulfonyl) -ethylamide hydrochloride. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 95 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 18.4 parts of 2,4,6-trichloro-1,3,5-triazine are added. The reaction mixture is stirred for a further 4 hours at a temperature of 3 to 5 ° C., keeping the pH at 1.7 to 2.2 by adding sodium bicarbonate. After 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was placed in 100 ml of water and the mixture adjusted to pH 5 was added, the pH of the reaction mixture was initially adjusted to During this period, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH is maintained at 5 to 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours. After the completion of the reaction, this intermediate product was treated with diazotized 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) at a temperature of 0 to 10 ° C and a pH of 6.5.
-Coupling with 33 parts of ethylamide hydrochloride. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 96 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 18.4 parts of 2,4,6-trichloro-1,3,5-triazine are added. The reaction mixture is stirred for a further 4 hours at a temperature of 3 to 5 ° C., keeping the pH at 1.7 to 2.2 by adding sodium bicarbonate. After 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was placed in 100 ml of water and the mixture adjusted to pH 5 was added, the pH of the reaction mixture was initially adjusted to During this period, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH is maintained at 5 to 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours. After completion of the reaction, this intermediate product was treated with diazotized 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl)-at a temperature of 0 to 10 ° C and a pH of 6.5.
Coupling with 33 parts of ethylamide hydrochloride. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 97 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 18.4 parts of 2,4,6-trichloro-1,3,5-triazine are added. The reaction mixture is stirred for a further 4 hours at a temperature of 3 to 5 ° C., keeping the pH at 1.7 to 2.2 by adding sodium bicarbonate. After 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was placed in 100 ml of water and the mixture adjusted to pH 5 was added, the pH of the reaction mixture was initially adjusted for a while. During this period, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH is maintained at 5 to 6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours. After completion of the reaction, the intermediate product was treated with diazotized 3-aminobenzoic acid-N'-γ- (β'-chloroethylsulfonyl) at a temperature of 0 to 10 ° C and a pH of 6.5.
-Coupling with 35 parts of propylamide hydrochloride. pH8
After completion of the coupling reaction at 1, the reaction mixture is clarified by filtration and the reaction dye of the formula below formed is isolated by concentrating the reaction solution at pH 7 or by freeze-drying.

This dye dyes cotton red.

Example 98 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 18.4 parts of 2,4,6-trichloro-1,3,5-triazine are added. The reaction mixture is stirred for a further 4 hours at a temperature of 3 to 5 ° C., keeping the pH at 1.7 to 2.2 by adding sodium bicarbonate. 100 parts of 35 parts of 4-aminobenzoic acid-N'-γ- (β'-chloroethylsulfonyl) -propylamide hydrochloride
After adding the mixture adjusted to pH 5 to the reaction mixture, the pH of the reaction mixture is kept constant at a low Congo acidity by adding 2N sodium hydroxide solution constantly for a while for the first time. Hold on. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours. After completion of the reaction, this intermediate product was coupled with 33 parts of diazotized 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride at a temperature of 0-10 ° C and a pH of 6.5. To do. pH
After completion of the coupling reaction at 8, the reaction mixture is clarified and the reaction dye of the formula below formed is isolated at pH 7 by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 99 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 18.4 parts of 2,4,6-trichloro 1,3,5-triazine are added. The reaction mixture is stirred for a further 4 hours at a temperature of 3 to 5 ° C., keeping the pH at 1.7 to 2.2 by adding sodium bicarbonate.
After 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was placed in 100 ml of water and the mixture adjusted to pH 5 was added, the pH of the reaction mixture was initially adjusted to During this period, 2N sodium hydroxide solution is constantly added to maintain weak Congo acidity, and then pH
Hold at 5 to 6. At this time, the temperature should be 20 for 2 to 3 hours
Raise to 25 ° C. After completion of the reaction, this intermediate product was treated with diazotized 4-aminobenzoic acid-N'-bis-β- (bis-β'-chloroethylsulfonyl) -ethylamide hydrochloride at a temperature of 0-10 ° C and pH 6.5. Coupling with the department. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 100 a) 1-amino-8-in a mixture of 1440 parts water and 720 parts ice.
To the suspension containing 255.2 parts of naphthol-3,6-disulfonic acid is added 155.2 parts of cyanuric chloride with good stirring.
The reaction mixture is kept stirring at a temperature of 3-5 ° C. for a further 4 hours while maintaining the pH at 1.7-2.2 with sodium bicarbonate.

b) Separately the diazonium salt of the diazo component is prepared: 285 parts of 4-aminobenzoic acid-N'- in 640 parts of water.
β- (β′-Chloroethylsulfonyl) -ethylamide hydrochloride is dissolved, and 105 parts by volume of 40% aqueous sodium nitrite solution is added to the solution adjusted to pH 6.7 to 6.8. This mixture is introduced into a mixture of 800 parts of crushed ice and 70 parts by volume of 95% aqueous sulfuric acid with good stirring. The mixture is further stirred at 0 to 5 ° C. for 1 hour, and then excess nitrous acid is decomposed with a small amount of amidosulfonic acid by a conventional method.

c) Combining the cyanuric chloride prepared in (a) above with the diazonium salt described in the primary condensate of aminonaphthol disulfonic acid (b). To carry out the coupling, the strongly acidic reaction mixture is adjusted to pH 4.0-4.5 with sodium bicarbonate at a temperature of about 5 ° C. and the temperature is raised to 15-20 ° C. Stirring is continued at this temperature and pH for a few more hours until the coupling is complete.

d) To the monoazo compound of (c) above, 640 parts of water with HClH ₂
Add 177 parts of NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl and adjust the pH to 5.5-6.0. The reaction mixture is heated to a temperature of 60-65 ° C. for 2 hours, maintaining the pH at about 6. The pH is then raised to 6.5-7.0 with sodium bicarbonate and the filtrate is spray dried.

Thus, 1100 parts of a powder containing sodium chloride having the following formula is obtained.

 This product dyes cotton red.

Example 101 a) 1-Amino-8-in a mixture of 1440 parts water and 720 parts ice.
To the suspension containing 255.2 parts of naphthol-3,6-disulfonic acid is added 155.2 parts of cyanuric chloride with good stirring.
The reaction mixture is kept stirring at 3-5 ° C. for a further 4 hours while maintaining the pH at 1.7-2.2 with sodium bicarbonate.

b) Separately, the diazonium salt of the diazo component is prepared: 285 parts of 3-aminobenzoic acid-N'- in 640 parts of water.
β- (β′-Chloroethylsulfonyl) -ethylamide hydrochloride is dissolved, and 105 parts by volume of 40% aqueous sodium nitrite solution is added to the solution adjusted to pH 6.7 to 6.8. This mixture is introduced into a mixture of 800 parts of crushed ice and 70 parts by volume of 95% aqueous sulfuric acid with good stirring. The mixture is further stirred at 0 to 5 ° C. for 1 hour, and then excess nitrous acid is decomposed with a small amount of amidosulfonic acid by a conventional method.

c) Combine the primary condensate of cyanuric chloride and aminonaphthol disulfonic acid prepared in (a) above with the diazonium salt solution described in (b). The strongly acidic reaction mixture for carrying out the coupling is adjusted to pH 4.0 to 4.5 with sodium bicarbonate at a temperature of about 5 ° C. and the temperature is raised to 15 to 20 ° C. Stirring is continued at this temperature and pH for a few more hours until the coupling is complete.

d) To the monoazo compound of (c) above, 640 parts of water with HClH ₂
Add 177 parts of NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl and adjust the pH to 5.5-6.0. The reaction mixture is heated to a temperature of 60-65 ° C. for 2 hours, maintaining the pH at about 6. The pH is then raised to 6.5-7.0 with sodium bicarbonate and the filtrate is spray dried.

Thus, about 1100 parts of a powder containing sodium chloride having the following formula is obtained.

 This product dyes cotton red.

Example 102 a) 1-amino-8-in a mixture of 1440 parts water and 720 parts ice.
To the suspension containing 255.2 parts of naphthol-3,6-disulfonic acid is added 155.2 parts of cyanuric chloride with good stirring.
The reaction mixture is kept stirring at 3-5 ° C. for a further 4 hours while maintaining the pH at 1.7-2.2 with sodium bicarbonate.

b) Separately the diazonium salt of the diazo component is prepared: 285 parts of 4-aminobenzoic acid-N'- in 640 parts of water.
β- (β′-Chloroethylsulfonyl) -ethylamide hydrochloride is dissolved, and 105 parts by volume of 40% aqueous sodium nitrite solution is added to the solution adjusted to pH 6.7 to 6.8. This mixture is introduced into a mixture of 800 parts of crushed ice and 70 parts by volume of 95% aqueous sulfuric acid. The mixture is further stirred at 0 to 5 ° C. for 1 hour, and then excess nitrous acid is decomposed with a small amount of amidosulfonic acid by a conventional method.

c) Combine the cyanuric chloride prepared in (a) above with the diazonium salt solution described in the primary condensate of aminonaphtholdisulfonic acid (b). To carry out the coupling, the strongly acidic reaction mixture is adjusted to pH 4.0-4.5 with sodium bicarbonate at a temperature of about 5 ° C. and the temperature is raised to 15-20 ° C. Stirring is continued at this temperature and pH for a few more hours until the coupling is complete.

d) In the monoazo compound of (c) above, in 640 parts of water Dissolve 312 parts and add a solution adjusted to pH 5.5 to 6.0. The reaction mixture is heated to a temperature of 60-65 ° C. for 2 hours, maintaining the pH at about 6. The pH is then raised to 6.5-7.0 with sodium bicarbonate and the filtrate is spray dried.

Thus, about 1100 parts of a powder containing sodium chloride having the following formula is obtained.

 This product dyes cotton red.

Example 103 a) 1-amino-8-in a mixture of 1440 parts water and 720 parts ice.
To the suspension containing 255.2 parts of naphthol-3,6-disulfonic acid is added 155.2 parts of cyanuric chloride with good stirring.
The reaction mixture is kept stirring at 3-5 ° C. for a further 4 hours while maintaining the pH at 1.7-2.2 with sodium bicarbonate.

b) Separately the diazonium salt of the diazo component is prepared: 285 parts of 4-aminobenzoic acid-N'- in 640 parts of water.
β- (β′-Chloroethylsulfonyl) -ethylamide hydrochloride is dissolved, and 105 parts by volume of 40% aqueous sodium nitrite solution is added to the solution adjusted to pH 6.7 to 6.8. This mixture is introduced into a mixture of 800 parts of crushed ice and 70 parts by volume of 95% aqueous sulfuric acid. The mixture is further stirred at 0 to 5 ° C. for 1 hour, and then excess nitrous acid is decomposed with a small amount of amidosulfonic acid by a conventional method.

c) Combining the cyanuric chloride prepared in (a) above with the diazonium salt described in the primary condensate of aminonaphthol disulfonic acid (b). To carry out the coupling, the strongly acidic reaction mixture is adjusted to pH 4.0-4.5 with sodium bicarbonate at a temperature of about 5 ° C. and the temperature is raised to 15-20 ° C. Stirring is continued at this temperature and pH for a few more hours until the coupling is complete.

d) To the monoazo compound of (c) above, 640 parts of water with HClH ₂
A solution of 240 parts of NCH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl dissolved and adjusted to pH 5.5 to 6.0 is added. The reaction mixture is heated to a temperature of 60-65 ° C. for 2 hours, maintaining the pH at about 6. The pH is then raised to 6.5-7.0 with sodium bicarbonate and the filtrate is spray dried.

Thus, about 1100 parts of a powder containing sodium chloride having the following formula is obtained.

This product dyes cotton red.

Example 104 1-Amino-8-naphthol-4,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 30 ° C. and add 42 parts of 2,4-dichloro-6-isopropoxytriazine dropwise. At this time, 2N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. 15 at this pH 4.0 to 4.5 and temperature of 65 ℃
Allow time to condense.

This solution is used as the coupling component for dye preparation.

To prepare the diazonium compound, 56 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride was suspended in 500 parts of ice-cold water, and concentrated hydrochloric acid was added.
Acidify by adding 5 parts 5N sodium nitrite solution 4
Diazotization occurs at 0 parts by volume. After stirring for 2 hours at approximately 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 105 4-Aminobenzoic acid-N'-bis-β- (bis-β '
-Chloroethylsulfonyl) -ethylamide hydrochloride 482
Pour parts into 1000 parts of water and carefully add 65 parts of sodium carbonate to form a solution. At this time, the pH is adjusted to 6.5 to 7.0. After stirring at this pH for another 2 hours, 750 parts ice and 31
% Hydrochloric acid and 255 parts are added. Then 173 parts of 40% aqueous sodium nitrite solution are added and stirred for a further 2 hours at 0-5 ° C. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was adjusted to pH 6.0 to 6.5 while simultaneously adding about 70 parts of sodium carbonate.
And cyanuric chloride, 1-amino-8-naphthol-4,
A solution of a secondary condensation product consisting of 1 mol each of 6-disulfonic acid and N-methyl-aniline is introduced. The method for producing this secondary condensation product is as follows.

1-amino-8-naphthol-4,6-disulfonic acid 319
Parts with stirring into a mixture of 500 parts of water and 121 parts of 33% caustic soda liquor. Adjust the pH of this solution to 6.5-7.0. After that, this solution is cyanuric chloride in 1 hour.
A suspension consisting of 194 parts, 800 parts of water and 800 parts of ice has a pH of 3.0 to 3.
Introduced in 8. 92 parts of sodium bicarbonate are dispersed and added, and the mixture is stirred at 0 to 5 ° C for 1 hour while maintaining this pH.

107 parts of N-methyl-aniline are added to the clear solution thus obtained and 115 parts of sodium carbonate are added in 1 hour to raise the pH value to 6.5 to 7.0. At this pH the temperature is 15
Stir for an additional 2 hours while maintaining at ~ 20 ° C.

After combining the diazonium salt suspension and the solution of the coupling component, the coupling mixture is stirred at room temperature for a further 2 hours. At this time, 70 parts of sodium carbonate is added little by little to maintain the pH at 6.0 to 6.5. After completion of coupling, heat to 50 ° C., add 40 parts of diatomaceous earth, clarify-filter the solution, and optionally add 50% disodium phosphate to the filtrate.
Add parts and spray dry.

A red powder is thus obtained which contains the electrolyte and optionally the buffer substances mentioned above. This includes alkali metal salts, especially sodium salts, of compounds of the formula:

The compound has very good dye properties. It is suitable for dyeing the various materials mentioned above, in particular for dyeing wool with acid baths or also for dyeing cellulose-containing fibrous materials in the presence of acid binders by the application and fixing methods known for reactive dyes. The dyed color is vivid red, the build-up property is good, and the fixing rate is high. The dyeings have very good wet fastnesses, for example excellent wash fastnesses.

Example 106 3-aminobenzoic acid-N'-bis-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride 327 parts to 100 parts
Suspend in 0 parts of water and make a neutral aqueous solution of pH 6.5.
About 600 parts of ice is added to this solution, and then about 200 parts of concentrated hydrochloric acid is slowly added with stirring until pH 2 is reached.

Then 173 parts of 40% aqueous sodium nitrite solution are added at a temperature of 0 to 5 ° C. and stirred for a further 1 hour. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was treated according to the procedure described in Example 1 with cyanuric chloride, 1-
A coupling reaction is carried out with a solution of a secondary condensation product consisting of 1 mol each of amino-8-naphthol-4,6-disulfonic acid and aminobenzene-3-sulfonic acid. After the coupling reaction is complete, the reaction solution is clarified and the dye is isolated, for example by spray drying or salting out with sodium chloride.

Thus, an electrolyte-containing red powder is obtained which contains the corresponding alkali metal salt of a compound of the formula:

This compound also has very good dye properties. Suitable for dyeing polyamide fiber materials, such as wool, in particular, or also for dyeing cellulosic fiber materials by the application and fixing processes known for dyes containing fiber-reactive groups, in particular .beta.-thiosulfatoethylsulfonyl groups. The color of the dyeing is a bright red, and the wet fastness, for example,
The wet fastnesses as described for the dyestuff of Example 1 are very good.

Example 107 4-aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) -ethylamide Hydrochloride 327 parts are put into 1000 parts of water, and 65 parts of sodium carbonate are carefully added to form a solution. . At this time, the pH is adjusted to 6.5 to 7.0. After stirring at this pH for a further 2 hours, 750 parts of ice and 255 parts of 31% hydrochloric acid are added. Then 173 parts of 40% aqueous sodium nitrite solution are added and stirred for a further 2 hours at 0-5 ° C. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was adjusted to pH 6.0 to 6.5 while simultaneously adding about 70 parts of sodium carbonate.
And cyanuric chloride, 1-amino-8-naphthol-4,
A solution of a secondary condensation product consisting of 1 mol each of 6-disulfonic acid and dicyanoethylamine is introduced. The method for preparing this secondary condensation product solution is as follows: 1-Amino-8-naphthol-4,6-disulfonic acid 319
Parts with stirring into a mixture of 500 parts of water and 121 parts of 33% caustic soda liquor. Adjust the pH of this solution to 6.5-7.0. After that, this solution is cyanuric chloride in 1 hour.
A suspension consisting of 194 parts, 800 parts of water and 800 parts of ice has a pH of 3.0 to 3.
Introduced in 8. 92 parts of sodium bicarbonate are dispersed and added, and the mixture is stirred at 0 to 5 ° C for 1 hour while maintaining this pH.

107 parts of N-methyl-aniline are added to the clear solution thus obtained and 115 parts of sodium carbonate are added in 1 hour to raise the pH value to 6.5 to 7.0. The temperature should be 15 at this pH.
Stir for an additional 2 hours while maintaining at ~ 20 ° C.

After combining the diazonium salt suspension and the solution of the coupling component, the coupling mixture is stirred at room temperature for a further 2 hours. At this time, 70 parts of sodium carbonate is added little by little to maintain the pH at 6.0 to 6.5. After completion of coupling, heat to 50 ° C, add 40 parts of diatomaceous earth, clarify the solution by filtration, and filter the filtrate, if necessary, with 50 mg of disodium phosphate.
Add parts and spray dry.

A red powder is thus obtained which contains the electrolyte and optionally the buffer substances mentioned above. This includes alkali metal salts, especially sodium salts, of compounds of the formula:

The compound has very good dye properties. It is suitable for dyeing the various materials mentioned above, in particular for dyeing wool with acid baths or also for dyeing cellulose-containing fibrous materials in the presence of acid binders by the application and fixing methods known for reactive dyes. The dyeing color is red and vivid, the build-up property is good and the fixing rate is high. The dyeings have very good wet fastnesses, for example excellent wash fastnesses.

Example 108 31.9 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid are neutrally dissolved in 800 ml of water and the solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At this time, 2N aqueous sodium hydroxide solution is added at the same time to maintain the pH at weak Congo acidity. After 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride were placed in 100 ml of water and the mixture adjusted to pH 5 was added, the first short 2N hydroxylation was performed. The pH of the reaction mixture is maintained at weak Congo acidity by the constant addition of sodium solution and then at pH 5-6.
At that time, the temperature is raised to 20 to 25 ° C in 2 to 3 hours. After the end of the reaction, this intermediate product is coupled at 0-10 ° C. and pH 6.5 with 33 parts of 3-aminobenzoic acid-N′-β- (β′-chloroethylsulfonyl) ethylamide hydrochloride.

After completion of the coupling reaction at pH 8, the reaction mixture is clarified by filtration, and the reactive dye of the formula below formed is isolated at pH 7 by concentrating the reaction solution or by freeze-drying.

 This dye dyes cotton red.

Example 109 4-aminobenzoic acid-N'-bis-β- (bis-β '
-Chloroethylsulfonyl) -ethylamide hydrochloride 482
Pour parts into 1000 parts of water and carefully add 65 parts of sodium carbonate to form a solution. At this time, the pH is adjusted to 6.5 to 7.0. After stirring at this pH for another 2 hours, 750 parts ice and 31
% Hydrochloric acid and 255 parts are added. Then 173 parts of 40% aqueous sodium nitrite solution are added and stirred for a further 2 hours at 0-5 ° C. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was adjusted to pH 6.0 to 6.5 while simultaneously adding about 70 parts of sodium carbonate.
And cyanuric chloride, 1-amino-8-naphthol-4,
A solution of a secondary condensation product consisting of 1 mol each of 6-disulfonic acid and N-methyl-aniline is introduced. The method for producing this secondary condensation product is as follows: 1-Amino-8-naphthol-3,6-disulfonic acid 319
Parts with stirring into a mixture of 500 parts of water and 121 parts of 33% caustic soda liquor. Adjust the pH of this solution to 6.5-7.0. After that, this solution is cyanuric chloride in 1 hour.
A suspension consisting of 194 parts, 800 parts of water and 800 parts of ice has a pH of 3.0 to 3.
Introduced in 8. 92 parts of sodium bicarbonate are dispersed and added, and the mixture is stirred at 0 to 5 ° C for 1 hour while maintaining this pH.

107 parts of N-methyl-aniline are added to the clear solution thus obtained and 115 parts of sodium carbonate are added in 1 hour to raise the pH value to 6.5 to 7.0. The temperature should be 15 at this pH.
Stir for an additional 2 hours while maintaining at ~ 20 ° C.

After combining the diazonium salt suspension and the solution of the coupling component, the coupling mixture is stirred at room temperature for a further 2 hours. At this time, 70 parts of sodium carbonate is added little by little to maintain the pH at 6.0 to 6.5. After completion of coupling, heat to 50 ° C, add 40 parts of diatomaceous earth, clarify the solution by filtration, and filter the filtrate, if necessary, with 50 mg of disodium phosphate.
Add parts and spray dry.

A red powder is thus obtained which contains the electrolyte and optionally the buffer substances mentioned above. This includes alkali metal salts, especially sodium salts, of compounds of the formula:

The compound has very good dye properties. It is suitable for dyeing the various materials mentioned above, in particular for dyeing wool in an acid bath or also for dyeing cellulosic fibrous materials in the presence of acid binders by the application and fixing methods known for reactive dyes. The dyeing color is red and vivid, the build-up property is good and the fixing rate is high. The dyeings have very good wet fastnesses, for example excellent wash fastnesses.

Example 110 327 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) -ethylamide hydrochloride are dissolved in 1000 parts of water and a neutral aqueous solution of pH 6.5 is prepared. About 600 parts of ice is added to this solution, and then about 200 parts of concentrated hydrochloric acid is slowly added with stirring until pH 2 is reached.

Then 173 parts of 40% aqueous sodium nitrite solution are added at a temperature of 0 to 5 ° C. and stirred for a further 1 hour. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was treated according to the procedure described in Example 1 with cyanuric chloride, 1-
A coupling reaction is carried out with an aqueous solution of a secondary condensation product consisting of 1 mol each of amino-8-naphthol-3,6-disulfonic acid and aminobenzene-3-sulfonic acid. After the coupling reaction is complete, the reaction solution is clarified and the dye is isolated, for example by spray drying or salting out with sodium chloride.

Thus, an electrolyte-containing red powder is obtained which contains the corresponding alkali metal salt of a compound of the formula:

This compound also has very good dye properties. Suitable for dyeing polyamide fiber materials, such as wool, in particular, or also for dyeing cellulosic fiber materials by the application and fixing processes known for dyes containing fiber-reactive groups, in particular .beta.-thiosulfatoethylsulfonyl groups. The color of the dyeing is a bright red, and the wet fastness, for example,
The wet fastnesses as described for the dyestuff of Example 1 are very good.

Example 111 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) -ethylamide 327 parts of water is put into 1000 parts of water, and 65 parts of sodium carbonate is carefully added to form a solution. . At this time, the pH is adjusted to 6.5 to 7.0. After stirring at this pH for a further 2 hours, 750 parts of ice and 255 parts of 31% hydrochloric acid are added. Then 173 parts of 40% aqueous sodium nitrite solution are added and stirred for a further 2 hours at 0-5 ° C. Then, excess nitrous acid is decomposed with amidosulfonic acid.

The diazonium salt suspension thus obtained was adjusted to pH 6.0 to 6.5 while simultaneously adding about 70 parts of sodium carbonate.
And cyanuric chloride, 1-amino-8-naphthol-3,
A solution of a secondary condensation product consisting of 1 mol each of 6-disulfonic acid and dicyanoethylamine is introduced. The method for producing this secondary condensation product solution is as follows: 1-Amino-8-naphthol-3,6-disulfonic acid 319
Parts with stirring into a mixture of 500 parts of water and 121 parts of 33% caustic soda liquor. Adjust the pH of this solution to 6.5-7.0. After that, this solution is cyanuric chloride in 1 hour.
A suspension consisting of 194 parts, 800 parts of water and 800 parts of ice has a pH of 3.0 to 3.
Introduced in 8. 92 parts of sodium bicarbonate are dispersed and added, and the mixture is stirred at 0 to 5 ° C for 1 hour while maintaining this pH.

107 parts of N-methyl-aniline are added to the clear solution thus obtained and 115 parts of sodium carbonate are added in 1 hour to raise the pH value to 6.5 to 7.0. The temperature should be 15 at this pH.
Stir for an additional 2 hours while maintaining at ~ 20 ° C.

After combining the diazonium salt suspension and the solution of the coupling component, the coupling mixture is stirred at room temperature for a further 2 hours. At this time, 70 parts of sodium carbonate is added little by little to maintain the pH at 6.0 to 6.5. After completion of coupling, heat to 50 ° C, add 40 parts of diatomaceous earth, clarify the solution by filtration, and filter the filtrate, if necessary, with 50 mg of disodium phosphate.
Add parts and spray dry.

A red powder is thus obtained which contains the electrolyte and optionally the buffer substances mentioned above. This includes alkali metal salts, especially sodium salts, of compounds of the formula:

The compound has very good dye properties. It is suitable for dyeing the various materials mentioned above, in particular for dyeing wool with acid baths or also for dyeing cellulose-containing fibrous materials in the presence of acid binders by the application and fixing methods known for reactive dyes. The dyed color is vivid red, the build-up property is good, and the fixing rate is high. The dyeings have very good wet fastnesses, for example excellent wash fastnesses.

Further useful reactive dyes of general formula (1A) shown in the following table were prepared according to the methods described in Examples 105-111 above. The symbols D ₁ , K and Z ₁ in the table have the meanings described in formula (1A). W _{1 to} W ₇ have the meanings given above. The colors listed in the last column of the table are the colors obtained when cotton is dyed with the corresponding dye.

Example 176 4-β-sulfatoethylsulfonyl-aniline 70.2
5 parts are poured into 325 parts water and dissolved using sodium bicarbonate at pH 5.3-6.0 at a temperature of 20-22 ° C. for 1 hour. Then 54 parts by volume of 31% hydrochloric acid and 225 parts of ice are added to make the solution congo acidic and the temperature adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Then a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. After that, 1-amino-8-hydroxynaphthalene-3,6-
Add 77.8 parts of disulfonic acid. This batch at 4-8 ° C
Stir for 4 to 5 hours at the same temperature and pH of 1 to 2. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 82 parts of 4-aminobenzoic acid-N'-β-
The (β'-chloroethylsulfonyl) -ethylamide hydrochloride is diazotized as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 177 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are charged into 325 parts water and pH 5.3 to 6.
It dissolves at 0 at a temperature of 20-22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Then a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Then, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid 77.
Add 8 parts. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, pH
Is adjusted to 6.0 with sodium carbonate.

In a separate batch, 70.25 parts of 4-β-sulfatoethylsulfonyl-aniline are diazotised as above.

The diazonium suspension thus obtained is added to the solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the diazo compound formed.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 178 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are charged to 325 parts water and pH 5.3 to 6. Using sodium bicarbonate.
It dissolves at 0 at a temperature of 20-22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. After that, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid 77.8
Add parts. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, pH
Is adjusted to 6.0 with sodium carbonate.

In a separate batch, 70.25 parts of 4-β-sulfatoethylsulfonyl-aniline are diazotised as above.
The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 179 4-β-sulfatoethylsulfonyl-aniline 70.2
5 parts are poured into 325 parts water and dissolved using sodium bicarbonate at pH 5.3-6.0 at a temperature of 20-22 ° C. for 1 hour. Then 54 parts by volume of 31% hydrochloric acid and 225 parts of ice are added to make the solution congo acidic and the temperature adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a small amount of excess nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After a while
77.8 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid are added. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 82 parts of 4-aminobenzoic acid-N'-β-
The (β'-chloroethylsulfonyl) -ethylamide hydrochloride is diazotized as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. After this, if necessary, after clear filtration, the reaction solution is evaporated and concentrated to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 180 3-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are charged to 325 parts water and bicarbonate is used to pH 5.3-6.0. temperature
Dissolve at 20-22 ° C over 1 hour. Next, 31% hydrochloric acid 54
The solution is acidified to Congo by adding parts by volume and 225 parts of ice and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Thereafter, a slight excess of nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After that, 1-amino-8
-Hydroxynaphthalene-3,6-disulfonic acid 77.8 parts are added. This batch is run at a temperature of 4-8 ° C and a pH of 1-2.
Stir for 4 to 5 hours. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 82 parts of 4-aminobenzoic acid-N'-β-
The (β'-chloroethylsulfonyl) -ethylamide hydrochloride is diazotized as above. The diazonium suspension obtained is then added to the solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 181 3-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are added to 325 parts water and pH 5.3 to 6. Using sodium bicarbonate.
It dissolves at 0 at a temperature of 20-22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a small amount of excess nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After that, 1-amino-8
-Hydroxynaphthalene-3,6-disulfonic acid 77.8 parts are added. This batch is run at a temperature of 4-8 ° C and a pH of 1-2.
Stir for 4 to 5 hours. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 82 parts of 4-aminobenzoic acid-N'-β-
The (β'-chloroethylsulfonyl) -ethylamide hydrochloride is diazotized as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. Then, if necessary, after clear filtration, the reaction solution is evaporated and concentrated to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 182 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts is charged to 325 parts water and pH 5.3 to 6. Using sodium bicarbonate.
It dissolves at 0 at a temperature of 20-22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Then a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Then, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid 77.
Add 8 parts. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, pH
Is adjusted to 6.0 with sodium carbonate.

In a separate batch 4-amino-benzoic acid-N'-β-
(Β'-Chloroethylsulfonyl) ethylamide hydrochloride
82 parts are diazotized as above.

The diazonium suspension thus obtained is added to the solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 183 4-β-sulfatoethylsulfonyl-aniline 70.2
5 parts are poured into 325 parts water and dissolved using sodium bicarbonate at pH 5.3-6.0 at a temperature of 20-22 ° C. for 1 hour. Then 54 parts by volume of 31% hydrochloric acid and 225 parts of ice are added to make the solution congo acidic and the temperature adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Thereafter, 77.8 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 3-amino-benzoic acid-N'-β-
(Β'-Chloroethylsulfonyl) ethylamide hydrochloride
82 parts are diazotized as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 184 3-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are charged to 325 parts water and pH 5.3 to 6. Using sodium bicarbonate.
It dissolves at 0 at a temperature of 20-22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a small amount of excess nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After that, 1-amino-8
-Hydroxynaphthalene-3,6-disulfonic acid 77.8 parts are added. This batch is run at a temperature of 4-8 ° C and a pH of 1-2.
Stir for 4 to 5 hours. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch, 4-β-sulfatoethylsulfonyl-
70.25 parts of aniline are diazotized in the same manner as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. After this, if necessary, after clear filtration, the reaction solution is evaporated and concentrated to isolate the produced diazo compound. Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 185 3-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide Hydrochloride 82 parts are charged to 325 parts water and bicarbonate is used to pH 5.3-6.0. temperature
Dissolve at 20-22 ° C over 1 hour. Next, 31% hydrochloric acid 54
The solution is acidified to Congo by adding parts by volume and 225 parts of ice and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Thereafter, a slight excess of nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After that, 1-amino-8
-Hydroxynaphthalene-4,6-disulfonic acid 77.8 parts are added. This batch is run at a temperature of 4-8 ° C and a pH of 1-2.
Stir for 4 to 5 hours. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch, 4-β-sulfatoethylsulfonyl-
70.25 parts of aniline are diazotized in the same manner as above. The diazonium suspension obtained is then added to the solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 186 4-β-sulfatoethylsulfonyl-aniline 70.2
5 parts are poured into 325 parts water and dissolved using sodium bicarbonate at pH 5.3-6.0 at a temperature of 20-22 ° C. for 1 hour. Then 54 parts by volume of 31% hydrochloric acid and 225 parts of ice are added to make the solution congo acidic and the temperature adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Thereafter, 77.8 parts of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid is added. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In another batch 3-amino-benzoic acid-N'-β-
(Β'-Chloroethylsulfonyl) ethylamide hydrochloride
82 parts are diazotized as above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 187 Disazo dye, 1-amino-2- [4'-benzoic acid-
N'-β- (β'-chloroethylsulfonylethylamide-phenylazo)]-7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid 82.0 parts neutral In the form of a solution and at a temperature of 0 to 5 ° C., it is reacted once with a suspension of 18.5 parts of cyanuric chloride, once dissolved in 110 parts of acetone and reprecipitated with 250 parts of ice. This reaction is carried out at pH 6.0 to 6.5 and during the reaction 2
50 parts of normal soda solution is added dropwise to maintain this pH. Then 3-amino-benzoic acid-N'-β- (β 'in the form of a powder
Add 32 parts of chloroethylsulfonyl) ethylamide hydrochloride and heat to 20-30 ° C. At this time, 100 parts of 2N soda solution is added dropwise to maintain the pH at 6.0 to 6.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 188 Disazo dye, 1-amino-2- [3'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo)]-7- (2 "-sulfo-5"-
Aminophenylazo) -8-naphthol-3,6-disulfonic acid (82.0 parts) was added in the form of a neutral solution and at a temperature of 0 ° C. to 2,4,6-trifluoro-1,3,5-triazine (14.2 parts).
Incubate for 20 minutes. This reaction is carried out at pH 6.0 to 6.5, and 50 parts of 2N soda solution is added dropwise during the reaction to maintain this pH. Then 4-amino-benzoic acid-N'in powder form
Add 32 parts of -β- (β'-chloroethylsulfonyl) ethylamide hydrochloride and heat to 0-10 ° C. At this time 2
100 parts of normal soda solution is added dropwise to maintain the pH at 5.0 to 6.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 189 Disazo dye, 1-amino-2- [4'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo] -7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid 82.0 parts as a neutral solution And in the form of a solution of 18.5 parts of cyanuric chloride once dissolved in 110 parts of acetone and reprecipitated with 250 parts of ice at a temperature of 0 to 5 ° C. This reaction is carried out at pH 6.0 to 6.5 and during the reaction 2
50 parts of normal soda solution is added dropwise to maintain this pH. Then 17.3 parts of 3-aminobenzenesulfonic acid in powder form are added and heated to 20-30 ° C. 2N soda solution
100 parts is added dropwise to maintain the pH at 6.0 to 6.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 190 Disazo dye, 1-amino-2- [3'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo] -7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid 82.0 parts as a neutral solution And in the form of a solution of 18.5 parts of cyanuric chloride once dissolved in 110 parts of acetone and reprecipitated with 250 parts of ice at a temperature of 0 to 5 ° C. This reaction is carried out at pH 6.0 to 6.5 and during the reaction 2
50 parts of normal soda solution is added dropwise to maintain this pH. Then 0.8 parts of HCl H ₂ NCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl _{2 in} powder form are added and heated to 20-30 ° C. At this time, 100 parts of 2N soda solution is added dropwise to maintain the pH at 6.0 to 6.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 191 Disazo dye, 1-amino-2- [4'-benzoic acid-
N'-γ- (β'-chloroethylsulfonyl) propylamido-phenylazo] -7- (2 "-sulfo-5"-
Aminophenylazo) -8-naphthol-3,6-disulfonic acid 83 parts was once dissolved in 110 parts acetone in the form of a neutral solution and at a temperature of 0 to 5 ° C and reprecipitated with 250 parts ice. React with 18.5 parts suspension of cyanuric chloride. This reaction is carried out at pH 6.0 to 6.5 and during the reaction 2
50 parts of normal soda solution is added dropwise to maintain this pH.

The resulting dye of the following structural formula is isolated by salting out or spray drying.

Example 192 Disazo dye, 1-amino-2- [4'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo] -7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid in the form of a neutral solution And, at a temperature of 20 to 25 ° C., 2,4-dichloro-6-isopyropoxy-triazine 2
React with 1.0 part suspension. This reaction is pH 6.0 to 6.5
This was done by dropping 50 parts of 2N soda solution during the reaction.
Maintain pH.

The dyestuff of the formula below formed is isolated by salting out or spray drying.

Example 193 Disazo dye, 1-amino-2- [4'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo] -7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid in the form of a neutral solution At a temperature of 0 ° C at 2,4,6-
It is reacted with 14.2 parts of trifluoro-1,3,5-triazine for 20 minutes. This reaction is carried out at pH 6.0 to 6.5, and 50 parts of 2N soda solution is added dropwise during the reaction to maintain this pH. Then 17.3 parts of 3-aminobenzenesulfonic acid in powder form are added and heated to 0 to 20 ° C. At this time, 100 parts of 2N soda solution is added dropwise to maintain the pH at 6.0 to 6.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 194 Disazo dye, 1-amino-2- [3'-benzoic acid-
N'-β- (β'-chloroethylsulfonyl) ethylamido-phenylazo] -7- (2 "-sulfo-5" -aminophenylazo) -8-naphthol-3,6-disulfonic acid 82.0 parts as a neutral solution At a temperature of 0 ° C in the form of 2,
Incubate with 14.2 parts of 4,6-trifluoro-1,3,5-triazine for 20 minutes. This reaction is carried out at pH 6.0 to 6.5, and 50 parts of 2N soda solution is added dropwise during the reaction to maintain this pH. Then HClH ₂ N CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl 2 in powder form
Add 5.2 parts and heat to 0-10 ° C. At this time, 100 parts of 2N soda solution is added dropwise to maintain the pH at 4.0 to 4.5.

This gives a dye of the structural formula below, which is isolated by salting out or spray drying.

Example 195 4-aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide 33 parts of a neutral solution dissolved in 150 parts of water and 20.3 parts by volume of 5N aqueous sodium nitrite solution The mixture is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

Then, for the coupling reaction, a solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The coupling pH is maintained at 1.5 to 2.5 with sodium acetate. After completion of this first coupling, the produced monoazo compound is reacted with a diazonium salt solution to carry out a second coupling reaction. This diazonium salt solution is manufactured as follows. : 1,3-diaminobenzene-4-sulfonic acid 18.8 parts to 200
Part of water and neutralize with sodium carbonate. To this, 23 parts of 2,4,5,6-tetrachloropyrimidine is added dropwise at 50 to 60 ° C. over 8 hours. During this time the pH is maintained at 6.0 with 2N NaOH and the temperature does not exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual. The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. After this, as described above, the monoazo compound solution and pH
Coupling at 5.5 to 6.5. The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 196 Consists of a neutral solution prepared by dissolving 33 parts of 3-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) ethylamide hydrochloride in 150 parts of water and 20.3 parts by volume of 5N aqueous sodium nitrite solution. The mixture is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

Then, for the coupling reaction, a solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The coupling pH is maintained at 1.5 to 2.5 with sodium acetate. After completion of this first coupling, the produced monoazo compound is reacted with a diazonium salt solution to carry out a second coupling reaction. This diazonium salt solution is prepared as follows: 200 parts of 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid
Part of water and neutralize with sodium carbonate. To this, 23 parts of 2,4,5,6-tetrachloropyrimidine is added dropwise at 50 to 60 ° C. over 8 hours. During this time the pH is maintained at 6.0 with 2N NaOH and the temperature does not exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual. The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. After this, as described above, the monoazo compound solution and pH
Coupling at 5.5 to 6.5. The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 197 4-Aminobenzoic acid-N '-[gamma]-([beta]'-chloroethylsulfonyl) propylamide 34 parts of a neutral solution in which 150 parts of water was dissolved and 5N aqueous sodium nitrite solution 20.3
The mixture consisting of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice is introduced with stirring at a temperature of 0 to 5 ° C. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

Then, for the coupling reaction, a solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The coupling pH is maintained at 1.5 to 2.5 with sodium acetate. After completion of this first coupling, the produced monoazo compound is reacted with a diazonium salt solution to carry out a second coupling reaction. This diazonium salt solution is prepared as follows: 200 parts of 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid
Part of water and neutralize with sodium carbonate. To this, 23 parts of 2,4,5,6-tetrachloropyrimidine is added dropwise at 50 to 60 ° C. over 8 hours. During this time the pH is maintained at 6.0 with 2N NaOH and the temperature does not exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual. The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. After this, as described above, the monoazo compound solution and pH
Coupling at 5.5 to 6.5. The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 198 Consists of a neutral solution prepared by dissolving 33 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) ethylamide hydrochloride in 150 parts of water and 20.3 parts by volume of 5N aqueous sodium nitrite solution. The mixture is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

Then, for the coupling reaction, a solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The coupling pH is maintained at 1.5 to 2.5 with sodium acetate. After completion of this first coupling, the produced monoazo compound is reacted with a diazonium salt solution to carry out a second coupling reaction. This diazonium salt solution is prepared as follows: 200 parts of 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid
Part of water and neutralize with sodium carbonate. To this, 18 parts of 5-chloro-2,4,6-trifluoropyrimidine is added dropwise at 20 to 30 ° C over 8 hours. During this time, adjust the pH with 2N NaOH
Hold at 6.0 and do not let the temperature exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate was acidified by adding 35 parts by volume of 31% hydrochloric acid, and then 500 parts of ice was added thereto, followed by 5
Diazotize by slowly adding 20 parts by volume of a specified aqueous sodium nitrite solution. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual. This diazonium salt suspension was adjusted to pH 5 with 17.8 parts of sodium bicarbonate.
Adjust to 5 to 6.5. This is followed by coupling with the monoazo compound solution at pH 5.5-6.5 as described above. The resulting disazo compound is salted out with sodium chloride, suction filtered and dried. Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 199 3-aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide 33 parts of a neutral solution in 150 parts of water and a 5N sodium nitrite aqueous solution (20.3 parts by volume) The mixture is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

Then, for the coupling reaction, a solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The coupling pH is maintained at 1.5 to 2.5 with sodium acetate. After completion of this first coupling, the produced monoazo compound is reacted with a diazonium salt solution to carry out a second coupling reaction. This diazonium salt solution is prepared as follows: 200 parts of 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid
Part of water and neutralize with sodium carbonate. To this, 18 parts of 5-chloro-2,4,6-trifluoropyrimidine is added dropwise at 50-60 ° C over 8 hours. During this time, adjust the pH with 2N NaOH
Keep at 6.0 and do not let the temperature exceed 65 ° C.
After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual. The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. This is followed by coupling with the monoazo compound solution at pH 5.5-6.5 as described above. The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 200 1,3-Diaminobenzene-4-sulfonic acid 18.8 parts to 200
Part of water and neutralize with sodium carbonate. 23 parts of 2,4,5,6-tetrachloropyrimidine are added dropwise thereto at 50 to 60 ° C. within 1 hour. During this time the pH is maintained at 6.0 with 2N NaOH and the temperature does not exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual.

After this, due to the coupling reaction, 1-amino-8-
A solution of 31.9 parts of naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The pH of the coupling is kept between 2 and 3.0 with soda. After the completion of the primary coupling reaction, the produced monoazo compound is reacted with a diazonium salt solution to carry out a secondary coupling reaction. The diazonium salt solution is prepared as follows: 4-Aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide hydrochloride 33 parts dissolved in 150 parts water and a 5N neutral solution. A mixture of 20.3 parts by volume of aqueous sodium nitrite solution is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. This is followed by coupling with the monoazo compound solution at pH 5.5-6.5 as described above.
The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Example 201 1,3-Diaminobenzene-4-sulfonic acid 18.8 parts to 200
Part of water and neutralize with sodium carbonate. 2,4,6-trichloropyrimidine 18 at 20 to 30 ℃ within 1 hour
Parts are dripped. During this time the pH is maintained at 6.0 with 2N NaOH and the temperature does not exceed 65 ° C. After the condensation is complete, the fine suspension is filtered and washed with a 5% sodium chloride solution. The filtrate is acidified by adding 35 parts by volume of 31% hydrochloric acid, 500 parts of ice is added thereto, and then 20 parts by volume of a 5N sodium nitrite aqueous solution is slowly added to diazotize. After this, excess nitrous acid is decomposed with some amidosulfonic acid as usual.

After this, due to the coupling reaction, 1-amino-8-
A solution of 31.9 parts of naphthol-3,6-disulfonic acid dissolved in 500 parts of water and adjusted to pH 4 with hydrochloric acid is added. The pH of the coupling is kept between 2 and 3.0 with soda. After the completion of the primary coupling reaction, the produced monoazo compound is reacted with a diazonium salt solution to carry out a secondary coupling reaction. The diazonium salt solution is prepared as follows: 3-Aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) ethylamide 33 parts neutral solution of 5 parts dissolved in 150 parts water and 5N. A mixture of 20.3 parts by volume of aqueous sodium nitrite solution is introduced into a mixture of 26 parts by volume of 31% hydrochloric acid and 150 parts of ice at a temperature of 0 to 5 ° C. with stirring. The resulting suspension is stirred for another hour and then excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt suspension is adjusted to pH 5.5-6.5 with 17.8 parts of sodium bicarbonate. This is followed by coupling with the monoazo compound solution at pH 5.5-6.5 as described above.
The resulting disazo compound is salted out with sodium chloride, suction filtered and dried.

Thus, an alkali metal salt of a compound of the following formula is obtained in the form of a black powder containing an electrolyte.

This compound exhibits very good dye properties and is capable of dyeing and printing cellulosic fibrous materials in a marine blue color by the known and customary application and fixing techniques. Its fastness to use and fastness to processing are very good.
When wool is dyed from a weakly acidic bath, a marine blue dyeing product having excellent wet fastness after ammonia treatment can be obtained.

Further dyes listed in the following table were prepared according to the method described above (Examples 176-201). Each of these dyes dyes cotton in the colors shown in the table.

Example 372 1-Amino-4-β- (β′-chloroethylsulfonyl) -ethylaminocarbonylbenzene-2-sulfonic acid 37 parts of hydrochloric acid acid diazotization solution at a temperature of 0 to 5 ° C.
Coupling is carried out at pH 5 to 6 with a solution of 29.9 parts of 1- (2'-sulfo-5'-aminophenyl) -3-carboxy-5-pyrazolone. The yellow monoazo dye formed is then added with a suspension of 18.8 parts of cyanuric chloride and acylated at pH 6.

The chlorotriazine dye corresponding to the formula below formed is isolated.

Example 373 195 parts of cyanuric chloride are dissolved in 800 parts by volume of acetone. While stirring this solution well, 1300 parts of water, crushed ice 13
Place in a mixture consisting of 00 parts and 20 parts by volume of 2N hydrochloric acid. To the obtained suspension, 239 parts of 2-amino-5-naphthol-7-sulfonic acid, 65 parts of sodium carbonate and 200 parts of water were added.
50 to 6 with stirring in 0 parts pH 6.9 to 7.2 solution
Add in 0 minutes. The reaction of cyanogen chloride with aminonaphthol is carried out at 0-5 ° C and pH 3-5. Stirring is continued until free amine is no longer detected by the diazotised sample.

To the coupling component solution prepared above is added 370 parts of diazotised 1-amino-4-β- (β′-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-sulfonic acid. Stir for 2 hours while gradually adding sodium carbonate to raise the pH to 6.5-7.0. this
Stir for an additional hour at pH and room temperature. Next, 173 parts of aniline-m-sulfonic acid is added, and further about 110 parts of sodium carbonate is added little by little to maintain the pH at 5.5 to 6.0. The reaction solution is heated to 50 ° C. and kept at this temperature for 1 hour with stirring. After cooling the reaction solution, the azo compound formed is precipitated by adding sodium chloride, isolated by suction filtration and dried at 60 ° C. in vacuo.

Thus, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This azo compound is a very excellent dye. Due to its fiber reactivity it is possible to dye cotton in vivid orange shades, for example from aqueous-alkaline baths, by customary exhaust and pad processes. The color has very good washfastness and lightfastness.

Example 374 1-Amino-8-naphthol-3,6-disulfonic acid 64
800 parts at pH 5.0 by adding 30% sodium hydroxide aqueous solution
Soluble in water. Heat to 30 ° C. and add 42 parts of 2,4-dichloro-6-isopropoxy-triazine dropwise.
At this time, 2N sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. Condensate for 15 hours at this pH of 4.0 to 4.5 and temperature of 65 ° C.

This solution is used as the coupling component for dye preparation.

1-amino-4-β for producing a diazonium compound
74 parts of-(β'-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulfonic acid was suspended in 500 parts of ice-cold water, and 45 parts of concentrated hydrochloric acid was added to acidify the solution, and 5N sodium nitrite solution 40 Diazotization in the capacity part. After stirring for 2 hours at 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The reactive dyestuffs dye the cellulosic fiber materials in a bluish red color with very good wet fastness by the customary dyeing and printing processes.

Example 375 1-Amino-8-naphthol-3,6-disulfonic acid 64
Parts are added with 30% aqueous sodium hydroxide solution and pH 9.0
It dissolves in 800 parts of water at 9.5 to 9.5. Cool down to 10 ℃ 2,4,
34 parts of 6-trifluoro-5-chloro-pyrimidine are added dropwise. At this time, 5N sodium hydroxide solution was added dropwise to adjust the pH.
Keep at 9.25 to 9.5. Add this solution to pH 8.5 to 9
At 15 ° C. for 15 minutes and then 4N hydrochloric acid is added until the pH is 6.5.

This solution is used as the coupling component for dye preparation.

1-amino-4-β for producing a diazonium compound
74 parts of-(β'-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulfonic acid was suspended in 500 parts of ice-cold water, and 45 parts of concentrated hydrochloric acid was added to acidify the solution, and 5N sodium nitrite solution 40 Diazotization in the capacity part. After stirring for 2 hours at 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 376 1-Amino-8-naphthol-3,6-disulfonic acid 64
Parts are added 30% aqueous sodium hydroxide solution and pH 5.0
Dissolves in 800 parts of water. Heat to 60 ° C and 2,4,5,6
45 parts of tetrachlor-pyrimidine are added dropwise. At this time 5
The normal sodium hydroxide solution is added dropwise to maintain the pH at 4.0 to 4.5. Condensate for 15 hours at this pH of 4.0 to 4.5 and temperature of 65 ° C.

This solution is used as the coupling component for dye preparation.

1-amino-4-β for producing a diazonium compound
74 parts of-(β'-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulfonic acid was suspended in 500 parts of ice-cold water, and 45 parts of concentrated hydrochloric acid was added to acidify the solution, and 5N sodium nitrite solution 40 Diazotization in the capacity part. After stirring for 2 hours at 5 ° C., excess nitrous acid is destroyed with amidosulfonic acid.

The diazonium salt solution thus obtained is slowly added to the above coupling component solution at pH 5.5 to 6.0. Continue stirring for 2 hours until the coupling is complete. Sodium bicarbonate is added to maintain the pH at 5.5-6.0. The dyestuff is then precipitated by adding sodium chloride, isolated by suction filtration and dried at 40 ° C. in vacuo. After milling, a red electrolyte-containing powder is obtained. It contains the sodium salt of a compound of the formula:

This compound has very good dye properties,
The cellulosic fiber materials are dyed in bluish red with very good wet fastness by the dyeing and printing processes customary for reactive dyes.

Example 377 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are neutrally dissolved in 800 ml of water. The solution is cooled to 0-5 ° C. At this temperature 14.2 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise over 20 minutes. At the same time, 2N sodium hydroxide solution is added at the same time to maintain the pH of the reaction solution at weak Congo acidity. After adding 11 parts of N-methylaniline to 100 parts of water and adding a mixture adjusted to pH 5, the pH of the reaction mixture was constantly added with 2N sodium hydroxide solution for a while for a while for weak Congo acidity. And then pH 5-6. At this time, the temperature is raised to 20 to 25 ° C. in 2 to 3 hours.

After completion of the reaction, this intermediate product was diazotized 1-amino-4-β- (β'-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulfonic acid at a temperature of 0-10 ° C and pH 6.5. Coupling with the department. After completion of the coupling reaction at pH 8, the reaction mixture is clarified and the reaction dye of the formula below formed at pH 7 is isolated by concentrating the reaction solution or by freeze-drying.

This dye dyes cotton red.

Example 378 The example vinylates an aqueous solution of dye 377 at room temperature and pH 10 for about 30 minutes. When finished, readjust its pH to 6.5 with hydrochloric acid. The monoazo dye formed is isolated. This is a compound of formula

This dye dyes cotton red.

Example 379 a) 1-amino-8-in a mixture of 1440 parts water and 720 parts ice.
To the suspension containing 255.2 parts of naphthol-3,6-disulfonic acid is added 155.2 parts of cyanuric chloride with good stirring.
Continue stirring at 3-5 ° C for an additional 4 hours while maintaining the pH at 1.7-2.2 with sodium bicarbonate.

b) Separately the diazonium salt of the diazo component is prepared: i.e. 296 parts of 1-amino-4-β- (β 'in 640 parts of water.
-Chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulfonic acid is dissolved, and 105 parts by volume of 40% aqueous sodium nitrite solution is added to the solution adjusted to pH 6.7 to 6.8. This mixture was mixed with 800 parts of crushed ice and 70% of 95% aqueous sulfuric acid.
Introduce into mixture with volume. The mixture is further stirred at 0 to 5 ° C. for 1 hour, and then excess nitrous acid is decomposed with a small amount of amidosulfonic acid by a conventional method.

c) Combine the primary condensate of cyanuric chloride and aminonaphthol disulfonic acid prepared in (a) above with the diazonium salt prepared in (b). To carry out the coupling, the strongly acidic reaction mixture is adjusted to pH 4.0-4.5 with sodium bicarbonate at a temperature of about 5 ° C. and the temperature is raised to 15-20 ° C. Stirring is continued at this temperature and pH for a few more hours until the coupling is complete.

d) To the monoazole compound of (c) above, 640 parts of water and HCl.
H ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl
Add solution adjusted to 6.0. The reaction mixture is heated to a temperature of 60-65 ° C. for 2 hours, maintaining the pH at about 6. The pH is then raised to 6.5-7.0 with sodium bicarbonate and the filtrate is spray dried.

Thus, about 1100 parts of a powder containing sodium chloride having the following formula is obtained.

 This product dyes cotton red.

Example 380 An aqueous solution of the dye of Example 379 is vinylated at room temperature and pH 10 for about 40 minutes. When finished, readjust its pH to 6.0 with hydrochloric acid. The monoazo dye formed is isolated by spray drying.
This corresponds to the compound of the formula:

This dye dyes cotton in a red color with excellent dyeing fastness.

Example 381 4-β-sulfatoethylsulfonyl-aniline 70.2
5 parts are poured into 325 parts water and dissolved using sodium bicarbonate at pH 5.3 to 6.0 and temperature 22 to 22 ° C. for 1 hour. Then 54 parts by volume of 31% hydrochloric acid and 225 parts of ice are added to make the solution congo acidic and the temperature adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. After this, a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Thereafter, 77.8 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In a separate batch 1-amino-4-β- (β'-chloroethylsulfonyl) ethylaminocarbonyl-benzene-
92 parts of 2-sulfonic acid are diazotized in the same manner as above.
The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 382 An aqueous solution of the dye of Example 381 is vinylated at room temperature and pH 10 for about 30 minutes. After that, the pH is readjusted to 5.0 with hydrochloric acid. The monoazo dye formed is isolated by spray drying.
This corresponds to the compound of the formula:

This dye dyes cotton in a red color with excellent dyeing fastness.

Example 383 82 parts of 4-aminobenzoic acid-N'-β- (β'-chloroethylsulfonyl) ethylamide hydrochloride are charged to 325 parts of water and pH 5.3 to 6.
It dissolves at a temperature of 22 to 22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out at this temperature using 32.75 parts by volume of 40% aqueous sodium nitrite solution. Then a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. Then, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid 77.
Add 8 parts. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, pH
Is adjusted to 6.0 with sodium carbonate.

In a separate batch 80 parts of 4-β-sulfatoethylsulfonyl-2-sulfo-aniline are diazotized in the same manner as above.

The diazonium suspension thus obtained is added to the solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compound dyes cotton in a marine blue color which has very good dyeing fastness.

Example 384 82 parts of 4-aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide hydrochloride are added to 325 parts of water and pH 5.3 to 6. Using sodium bicarbonate.
It dissolves at a temperature of 22 to 22 ° C for 1 hour. Next 31
The solution is made acidic by Congo by adding 54 parts by volume of hydrochloric acid and 225 parts of ice, and the temperature is adjusted to 0-5 ° C. The diazotization is carried out using 32.75 parts by volume of 40% aqueous sodium nitrite solution at this temperature. After this, a slight excess of nitrous acid is destroyed with 0.5 part of amidosulfonic acid. After that, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid 77.8
Add parts. The batch is stirred for 4-5 hours at a temperature of 4-8 ° C. and a pH of 1-2. After this reaction time has elapsed, pH
Is adjusted to 6.0 with sodium carbonate.

In a separate batch, 92 parts of 1-amino-4-β- (β'-chloroethylsulfonyl) ethylaminocarbonyl-benzene-2-sulphonic acid are diazotised as described above. The diazonium suspension obtained is added to a solution of the monoazo compound prepared above. The reaction mixture is stirred for a further 3 hours, keeping the pH at 6-7. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound.

Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Example 385 82 parts of 3-aminobenzoic acid-N '-[beta]-([beta]'-chloroethylsulfonyl) ethylamide hydrochloride are charged into 325 parts of water and pH 5.3 to 6.0 using bicarbonate. temperature
Dissolve at 22-22 ° C over 1 hour. Next, 31% hydrochloric acid 54
The solution is acidified to Congo by adding parts by volume and 225 parts of ice and the temperature is adjusted to 0-5 ° C. The diazotization is carried out using 32.75 parts by volume of 40% aqueous sodium nitrite solution at this temperature. Thereafter, a slight excess of nitrous acid is decomposed with 0.5 part of amidosulfonic acid. After that, 1-amino-8
-Hydroxynaphthalene-3,6-disulfonic acid 77.8 parts are added. This batch is run at a temperature of 4-8 ° C and a pH of 1-2.
Stir for 4 to 5 hours. After this reaction time has elapsed, the pH is adjusted to 6.0 with sodium carbonate.

In a separate batch, 92 parts of 1-amino-4-β- (β'-chloroethylsulfonyl) -ethylaminocarbonyl-benzene-2-sulphonic acid are diazotised as described above. The diazonium suspension obtained is then added to the solution of the monoazo compound prepared above. pH 6 to 7
And the reaction mixture is stirred for a further 3 hours. In some cases, after clear filtration, the reaction solution is concentrated by evaporation to isolate the produced diazo compound. Thus, an electrolyte-containing black powder is obtained, which contains a sodium compound of the formula:

The compounds are very suitable as dyes for dyeing cellulosic fiber materials using the customary fixing methods according to the dyeing and printing processes known and customary for fiber-reactive dyes. This gives a marine blue dyed product having good fastness.

Reactive dyes of the formulas shown in the following table were further prepared according to the methods described in Examples 372 to 385 above.

Dyeing Example I 2 parts of the dye obtained in Example 1 are dissolved in 400 parts of water.
To this is added 1500 parts of a solution containing 53 g of sodium chloride per liter. Cotton fabric at 40 ℃ in this dye bath
Input 100 copies. After 45 minutes, a solution 100 containing 16 g of sodium hydroxide and 20 g of calcined soda per liter.
Parts are added. The temperature of the dyebath is kept at 40 ° C. for a further 45 minutes. The dyed fabric is then rinsed, nonionic detergent is added and boiled for 15 minutes to soap. Then wash and dry again.

Dyeing Example II 2 parts of the dye obtained in Example 1 are dissolved in 400 parts of water.
To this is added 1500 parts of a solution containing 53 g of sodium chloride per liter. Cotton fabric at 35 ℃ in this dye bath
Input 100 copies. After 20 minutes, a solution 100 containing 16 g of sodium hydroxide and 20 g of calcined soda per liter.
Parts are added. The temperature of the dyebath is kept at 35 ° C. for a further 15 minutes. Then raise the temperature to 60 ℃ in 20 minutes,
Hold at temperature for another 35 minutes. The dyed fabric is then rinsed, nonionic detergent is added and boiled for 15 minutes to soap. Then wash and dry again.

Dyeing Example III 8 parts of the reactive dye obtained in Example 1 are dissolved in 400 parts of water. 100 g of sodium sulfate per liter of this solution
1400 parts of a solution containing is added. 25 ℃ in this dye bath
Then add 100 parts of cotton fabric. After 10 minutes, 200 parts of a solution containing 150 g of trisodium phosphate per liter are added. Then the bath temperature is raised to 60 ° C. in 10 minutes and the temperature of the dyebath is kept at 60 ° C. for a further 90 minutes. The dyed fabric is then rinsed, nonionic detergent is added and boiled for 15 minutes to soap. Then wash and dry again.

Dyeing Example IV 4 parts of the reactive dye obtained in Example 1 are dissolved in 50 parts of water. 5g sodium hydroxide and 20g per liter
50 parts of a solution containing calcined soda and is added. The resulting solution is padded with a cotton fabric to a weight gain of 70%. This is wound on a winding rod and left at room temperature for 3 hours. The dyed fabric is then rinsed, nonionic detergent is added and boiled for 15 minutes to soap. Then wash and dry again.

Dyeing Example V 6 parts of the reactive dye obtained in Example 1 are dissolved in 50 parts of water. Add 16 g of sodium hydroxide and 0.0
A solution containing 4 liters of water glass (38 ° Be) and 5
Add 0 parts. Increase the weight of cotton fabric with the resulting solution 70
Pad up to%. It is rolled up and left at room temperature for 10 hours. After that, rinse the dyed fabric,
Add nonionic detergent and boil for 15 minutes to soap.
Then wash and dry again.

Dyeing Example VI 2 parts of the reactive dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. The solution thus obtained is impregnated with a cotton fabric up to a weight gain of 75%. Then it is dried. Next, this fabric was treated with 4 g of sodium hydroxide per liter.
Impregnate with a warm solution at 300C containing 300 g of sodium chloride and squeeze to a weight gain of 75%. The dyeing is steamed for 30 seconds at 100 to 102 ° C., rinsed and soaped for 15 minutes in a 0.3% boiling solution of nonionic detergent. After that, it is washed and dried.

Printing Example I 3 parts of the reactive dye obtained in Example 1 are dispersed in 100 parts of the original paste while stirring at high speed. This original paste is 5% sodium alginate paste 50 parts, water 27.8 parts, urea 20 parts,
It contains 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium bicarbonate. A cotton fabric is printed with the print paste obtained, dried, and the print is steamed in saturated steam at 102 ° C. for 2 minutes. The printed fabric is washed, optionally boiling soaped, washed again and then dried.

Printing Example II 5 parts of the reactive dye obtained in Example 1 is dispersed in 100 parts of the original paste while stirring at high speed. This original paste is 5% sodium alginate paste 50 parts, water 36.5 parts, urea 10 parts,
It contains 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts of sodium bicarbonate. The printing paste obtained (the stability of which meets the industrial standards) is used to print a cotton fabric, which is then dried and the print is placed in saturated steam.
Steam at 102 ° C for 8 minutes. The printed fabric is washed, optionally boiling soaped, washed again and then dried.

Claims (9)

[Claims] 1. A formula {In the formula, K is a residue of a benzene-based, naphthalene-based, phenylazonaphthalene-based or pyrazolone-based coupling component, U is -CO-, and R is a formula [Wherein Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acetoxyethyl, β-halogenethyl or vinyl, and a1k is a polymethylene group having 1 to 6 carbon atoms or its A branched isomer, Y is hydrogen, V is hydrogen, an alkyl group having 1 to 4 carbon atoms,
Or expression (Wherein Z, a1k and Y have the above meanings)], r is 1 or 2, X is a triazine or pyrimidine heterocyclic reactive group,
Or when K is a phenylazonaphthalene group, a halopropionyl or haloacryloyl group or a group -U-
R or —SO ₂ Z, where R, U and Z have the meanings given above, and the benzene group A is unsubstituted or additionally C _1-4 alkyl, C _1-4 alkoxy, halogen. ,
Substituted by hydroxy, carboxy and sulfo}. 2. A formula (Wherein R ₂ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy, halogen, hydroxy, carboxy or sulfo, and K, U, R, X and r are the claims. Reactive dyestuff according to claim 1, having the meaning described in 1.). 3. A formula Where R ₃ is hydrogen, or optionally substituted C
Reactive dyestuff according to claim 2), which means _1-4 alkyl, R ₂ , U, R, X having the meanings stated in claim 2. 4. A formula The reactive dye according to claim ₂ , wherein R ₂ , U, R and X have the meanings defined in claim 2. 5. A formula The reactive dye according to claim ₂ , wherein R ₂ , U, R and X have the meanings defined in claim 2. (6) (Wherein R ₄ represents 0 to 2 substituents selected from the group consisting of C _1-4 alkyl, C _1-4 alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X has the meaning given in claim 2). 7. A formula (Wherein R ₅ represents 0 to 2 substituents selected from the group consisting of C _1-4 alkyl, C _1-4 alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X has the meaning given in claim 2). 8. A formula (Wherein R ₅ represents 0 to 2 substituents selected from the group consisting of C _1-4 alkyl, C _1-4 alkoxy, halogen, carboxy or sulfo, and R ₂ , U, R, X has the meaning given in claim 2). 9. Formula {In the formula, K is a residue of a benzene-based, naphthalene-based, phenylazonaphthalene-based or pyrazolone-based coupling component, U is -CO-, and R is a formula [Wherein Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acetoxyethyl, β-halogenethyl or vinyl, and a1k is a polymethylene group having 1 to 6 carbon atoms or its A branched isomer, Y is hydrogen, V is hydrogen, an alkyl group having 1 to 4 carbon atoms,
Or expression (Wherein Z, a1k and Y have the above meanings)], r is 1 or 2, X is a triazine or pyrimidine heterocyclic reactive group,
Or when K is a phenylazonaphthalene group, a halopropionyl or haloacryloyl group or a group -U-
R or —SO ₂ Z, where R, U and Z have the meanings given above, and the benzene group A is unsubstituted or additionally C _1-4 alkyl, C _1-4 alkoxy, halogen. ,
A method for dyeing or printing cotton with a reactive dye of (substituted by hydroxy, carboxy and sulfo).